JP2015183073A - Durable transparent plate-like member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a durable transparent plate-like member using a polymer containing, as a monomer, β-phellandrene obtainable from microorganisms, plants, etc. as a carbon neutral material.SOLUTION: (1) A durable transparent plate-like member contains 50-100 mass%, relative to the total mass of the durable transparent plate-like member, of β-phellandrene polymer of a specific gravity of equal to or higher than 0.85 and lower than 1.0 and a glass transition temperature of 100°C or higher. (2) The number average molecular weight, Mn, of the β-phellandrene polymer is 40,000 or higher. (3) At least a part of olefinic carbon-carbon double bonds the β-phellandrene polymer has are hydrogenated. (4) The thickness of the durable transparent plate-like member is 0.5-500 mm.

Description

  The present invention relates to a durable transparent plate-like member using a β-ferrandylene polymer. More specifically, the present invention relates to a lightweight durable transparent plate member suitable for outdoor use.

  Conventionally, plate-like members made of transparent resins such as polymethyl methacrylate (PMMA) and polycarbonate (PC) have been used for roofs and windows of residential environment facilities. However, a plate-like member using PMMA has problems such as poor light transmission and light resistance, but poor mechanical strength and chemical resistance. In addition, plate-like members using PC have high mechanical strength, but have poor chemical resistance and may cause hydrolysis due to long-term use. There is a problem such as lowering.

  In addition, alicyclic polyolefins and cyclic polyolefins are known as highly transparent thermoplastic resins. Examples thereof include dicyclopentadiene-based ring-opening polymerization hydrogenated products, addition copolymers of norbornene or dicyclopentadiene and olefins (see Patent Document 1), and vinylcyclohexane-based polymers (see Patent Document 2). Among them, vinylcyclohexane polymers have high heat resistance, low water absorption, low specific gravity, and low birefringence, but they are brittle and have insufficient light resistance because they have bulky substituents in their side chains. There is no problem. Furthermore, cyclic polyolefins other than vinylcyclohexane polymers have high heat resistance and low water absorption, but have a large specific gravity and insufficient light resistance.

  Since the monomers used as raw materials for such alicyclic hydrocarbon polymers are petroleum-derived compounds, they meet today's needs for products that use carbon-neutral materials that suppress carbon dioxide emissions. I can't say I'm doing it.

  As carbon-neutral polymer materials, compounds that can be produced through biosynthetic pathways in living organisms have attracted attention. For example, a polymer having a glass transition point of 80 ° C. obtained by polymerizing β-pinene derived from terpene oil extracted from pine or the like has been proposed (Patent Document 3). However, in order to obtain a polymer having a high polymerization degree that exhibits practical strength using β-pinene as a monomer, it was necessary to polymerize in the presence of a bifunctional vinyl compound. Furthermore, it is necessary to make the polymerization temperature as low as -80 ° C to 0 ° C. In order to manufacture at a low cost and from the viewpoint of recent environmental problems, further improvement of reaction conditions and natural materials with good polymerization characteristics are required. Use was desired.

JP 2000-221328 A Japanese Patent Laid-Open No. 63-43910 Japanese Patent No. 5275633

  The present invention has been made in view of the above circumstances, and is a durable transparent plate using a polymer containing β-ferrandrene as a monomer, which is a material that can be obtained from microorganisms or plants as a carbon neutral material. A shaped member is provided.

＜３＞ 前記βフェランドレン重合体に、下記化学式（Ｉ−１）、（Ｉ−２）、（ＩＩ−１）及び（ＩＩ−２）で表されるβフェランドレン単位が合計５０質量％以上含有されていることを特徴とする前記＜１＞又は＜２＞に記載の耐久性透明板状部材。

＜４＞ 前記βフェランドレン重合体の数平均分子量Ｍｎが４万以上であることを特徴とする前記＜１＞〜＜３＞の何れか一項に記載の耐久性透明板状部材。
＜５＞ 前記βフェランドレン重合体が有するオレフィン性炭素−炭素二重結合の少なくとも一部が水素化されていることを特徴とする前記＜１＞〜＜４＞の何れか一項に記載の耐久性透明板状部材。
＜６＞ 前記βフェランドレン重合体の水素添加率が、７０％以上であることを特徴とする前記＜５＞に記載の耐久性透明板状部材。
＜７＞ 前記耐久性透明板状部材の厚さが、０．５ｍｍ〜５００ｍｍであることを特徴とする前記＜１＞〜＜６＞の何れか一項に記載の耐久性透明板状部材。 <1> A durable transparent plate-like member having a specific gravity of 0.85 or more and less than 1.0, and a β-ferrandylene polymer having a glass transition temperature of 100 ° C. or more. A durable transparent plate-like member comprising 50 to 100% by mass with respect to the total mass of
<2> The durability according to <1>, wherein the β-ferrandylene polymer is obtained by polymerizing at least one of β-ferrandolenes represented by the following chemical formulas (I) and (II): Transparent plate-like member.

<3> The β-ferrandolene units represented by the following chemical formulas (I-1), (I-2), (II-1) and (II-2) are added to the β-ferrandylene polymer in a total of 50% by mass or more. The durable transparent plate-like member according to <1> or <2>, which is contained.

<4> The durable transparent plate member according to any one of <1> to <3>, wherein the β-ferrandylene polymer has a number average molecular weight Mn of 40,000 or more.
<5> At least a part of the olefinic carbon-carbon double bond of the β-ferrandylene polymer is hydrogenated, as described in any one of <1> to <4>, Durable transparent plate member.
<6> The durable transparent plate-like member according to <5>, wherein a hydrogenation rate of the β-ferrandylene polymer is 70% or more.
<7> The durable transparent plate member according to any one of <1> to <6>, wherein the durable transparent plate member has a thickness of 0.5 mm to 500 mm.

  According to the present invention, it is excellent in chemical resistance, transparency, light weight, heat resistance and mechanical strength, and further has excellent properties such as high light resistance, low water absorption, low birefringence and low photoelasticity. A transparent plate-like member can be provided.

The first aspect of the present invention is a durable transparent plate member.
First, a method for producing a β-ferrandylene polymer that is a material of the present invention will be described.
<Method for Producing β Ferrandrene Polymer>
β-Ferlandene, which is a monomer constituting the β-ferrandylene polymer, may be extracted and purified from a living organism, or may be chemically synthesized from a petroleum-derived compound. For example, β-ferrandrene contained in essential oil obtained by steam distillation from plant seeds and roots may be used, or existing chemical substances are used as raw materials, and β-ferrandrene obtained by a known chemical synthesis method is used. Also good.

  For example, when using an existing chemical as a raw material, a known chemical synthesis method (Organic & Biomolecular Chemistry, 9 (7), 2433-2451, 2011) in which 4-Isopropylcyclohexanone is used as a starting material and synthesized via Crypron The resulting β-ferrandrene can be used.

  When chemical substances extracted from living organisms are used as materials, for example, plants or plants containing β-ferrandrene, such as Todomatsu, Ginger, Fennel, Neroli, Rosewood, Tomato, Lavender, Canadian Balsam, Angelica, etc. The extract from may be purified and used. In particular, it is preferable to use high-purity β-ferrandrene. In that case, the purity (pure content) can be increased by a method such as precision distillation or separation using a silica gel column.

  By using biologically-derived β-ferrandrene as a carbon neutral material, it is possible to reduce the environmental load in the production process and to reduce carbon dioxide emissions.

In order to increase the glass transition temperature Tg related to heat resistance by increasing the number average molecular weight Mn of β-ferrandylene polymer, a β-ferrandylene polymer was synthesized in order to achieve the purpose of obtaining excellent light transmission and mechanical strength. In this reaction system, it is preferable that the purity (pure content) of β-ferrandol in the reaction solution containing β-ferrandol is as high as possible. Further, the reaction system is more preferably a reaction system in which a compound having a double bond that interferes with the polymerization of β-ferrandrene is excluded as much as possible.
Particularly preferably, for example, a substance that reacts with a cis-type conjugated double bond such as a Diels-Alder reaction reagent is added, and a cis-type conjugated double bond substance other than β-ferrandrene is removed as an insoluble substance, thereby It is preferable to increase the purity, and it is preferable to increase the purity by combining with precision distillation or separation using a silica gel column.

  Specifically, the content of β-ferrandol, that is, the purity (pure content) of β-ferrandol is preferably 70% by mass or more, and 80% by mass or more with respect to the total mass of the polymerizable compound in the reaction solution. Is more preferably 90% by mass or more, more preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more. . The content may be 100% by mass. Here, “purity” does not mean optical purity that distinguishes optical isomers of β-ferrandolene, but simply chemical purity that does not distinguish optical isomers of β-ferrandylene. The “polymerizable compound” means a compound having a double bond polymerizable with β-ferrandolene.

In the present specification and claims, the purity of β-ferrandol used in the reaction is a value determined by the percentage of peak area of β-ferrandol by a gas chromatography (GC) method or a GC-MS method. .
For example, a β-ferrandrene reaction solution is diluted with a chloroform solution (for high-performance liquid chromatograph manufactured by Wako Pure Chemical Industries, Ltd., purity 99.7%) so as to be 1% by mass, and a gas chromatograph analyzer (HP6890 manufactured by HEWLETT PACKARD) is used. Series GC System). At this time, DB-5 (a capillary column made by Agilent Technologies, 30 m × 0.25 mm ID × 0.25 μ) was used as a column for component separation, and the column temperature: start 50 ° C., final 300 ° C., heating rate 15 It is preferable to measure at ° C / min and injection temperature: 300 ° C. The β-ferrandol peak can be identified from the β-ferrandol standard solution or MS spectrum. It is preferable that the pure amount of β-ferrandrene is calculated as an area ratio of β-ferrandrene, where the sum of the total areas of peaks having an area value of 1000 or more observed in the GC analysis is 100.

  By adding a Lewis acid as a catalyst and dispersing well in an organic solvent constituting the reaction solution, slowly dropping high-purity β-ferrandrene, starting cationic polymerization, and reacting for a predetermined time, The intended β-ferrandylene polymer can be obtained.

  In performing cationic polymerization by such a solution polymerization method, the concentration of β-ferrandylene as a monomer is preferably 1 to 90% by mass, more preferably 10 to 80% by mass, based on the total mass of the reaction solution. More preferably, it can be adjusted to 10 to 50% by mass. When the concentration is less than 1% by mass, the productivity is low, while when it exceeds 90% by mass, it is difficult to remove the heat of polymerization.

The type of organic solvent constituting the reaction solution is not particularly limited as long as it can dissolve β-ferrandrene, and a solvent used in conventional cationic polymerization can be applied. Among these, a solvent with little chain transfer is preferable. Examples of such a solvent include halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons from the viewpoint of solubility and reactivity under polymerization conditions of the polymer. More specifically, for example, halogenated carbonization such as methylene chloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, n-propyl chloride, 1-chloro-n-butane, 2-chloro-n-butane and the like. Hydrogen solvents; aromatic hydrocarbon solvents such as benzene, toluene, xylene, anisole; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, decalin, etc. Can be mentioned.
As the organic solvent, one organic solvent may be used alone, or two or more organic solvents may be used in combination.

The organic solvent may be a nonpolar solvent or a polar solvent.
In order to further increase the degree of polymerization of the β-ferrandylene polymer and obtain a tough polymer, it is particularly preferable to use a nonpolar solvent. Chlorinated solvents (solvents composed of compounds having chlorine atoms) such as halogenated aliphatic hydrocarbons and halogenated aromatic hydrocarbons can be used. However, since there are some chlorinated solvents that cannot be used from the viewpoint of disposal of waste solvents, desalting of polymerized products, and recent VOC regulations, it is not always preferable from the viewpoint of environmental problems.

As the Lewis acid, a Lewis acid used in conventional cationic polymerization is applicable. For example, EtAlCl ₂ , AlCl ₃ , Et ₂ AlCl, Et ₃ Al ₂ Cl ₃ , BCl ₃ , SnCl ₄ , TiCl ₄ , Ti (OR) _4-y Cl ₄ [R represents an alkyl group or an aryl group, and y represents an integer of 1 to 3. ] Is preferable because of high reactivity and selectivity. Other than these, metal halides such as BF ₃ , BBr ₃ , AlF ₃ , AlBr ₃ , TiBr ₄ , TiI ₄ , FeCl ₃ , FeCl ₂ , SnCl ₂ , WCl ₆ , MoCl ₅ , SbCl ₅ , TeCl ₂ , ZnCl _{2 , (i-Bu) 3 Al} , (i-Bu) 2 AlCl, (i-Bu) AlCl 2, Me 4 Sn, Et 4 Sn, Bu 4 Sn, Bu 3 metal alkyl compound such as SnCl [Me represents a methyl group Et represents an ethyl group and Bu represents a butyl group. _{], Al (OR) 3-} x Cl x [R represents an alkyl group or an aryl group, x is an integer of 1 or 2. And the like.
As the Lewis acid, one Lewis acid may be used alone, or two or more Lewis acids may be used in combination.

  As the polymerization catalyst, only the above-mentioned Lewis acid may be used, but an initiator used in combination as a Lewis acid may be used. In this case, the initiator is one that reacts with a Lewis acid to generate a carbon cation, and any initiator having such characteristics may be used. Specifically, alkyl vinyl ether-hydrogen chloride adduct, chloroalkyl vinyl ether-hydrogen chloride adduct, α-chloroethylbenzene, α-chloroisopropylbenzene, 1,3-bis (α-chloroisopropyl) benzene, 1,4- Bis (α-chloroisopropyl) benzene, 1,3-bis (α-chloroisopropyl) -5-t-butylbenzene, 1,3,5-tris (α-chloroisopropyl) benzene, t-butyl chloride, 2- Chlorine initiators such as chloro-2,4,4-trimethylpentane: alkyl vinyl ether-acetic acid adduct, α-acetoxyethylbenzene, α-acetoxyisopropylbenzene, 1,3-bis (α-acetoxyisopropyl) benzene, 1, Esters such as 4-bis (α-acetoxyisopropyl) benzene Agents, alpha-hydroxy ethylbenzene, alpha-hydroxy isopropylbenzene, 1,3-bis (alpha-hydroxy isopropyl) benzene, 1,4-bis (alpha-hydroxy isopropyl) alcohol initiator such as benzene.

Moreover, you may use the electron donor used with a living cationic polymerization catalyst. As such an electron donor, known ones can be used. Specifically, ethers such as diethyl ether (Et ₂ O), methyl-t-butyl ether, dibutyl ether: ethyl acetate (EtOAc), methyl acetate, isopropyl acetate, butyl acetate, methyl isobutyrate, ethyl isobutyrate, isobutyric acid Esters such as propyl; pyridine, 2-methylpyridine, 2,6-dimethylpyridine, 2,6-dibutylpyridine, 2,6-diphenylpyridine, 2,6-di-t-butylpyridine, 2,6- Examples thereof include pyridines such as di-t-butyl-4-methylpyridine; amines such as trimethylamine, triethylamine and tributylamine; amides such as dimethylacetamide and diethylacetamide; sulfoxides such as dimethylsulfoxide and the like. In particular, diethyl ether and methyl acetate are preferably used because they are economical and easy to remove after the reaction.

  The concentration of these Lewis acids in the reaction solution is preferably 0.001 to 100 parts by weight, more preferably 0.01 to 50 parts by weight, with respect to 100 parts by weight of β-ferrandolene added later. More preferably, it is 1 to 10 parts by weight. If the amount of the Lewis acid catalyst used is too small, the reaction may stop before the completion of the polymerization, and conversely if too large, it is uneconomical.

  The added β-ferrandrene may be previously dissolved in the same type of organic solvent as the organic solvent constituting the reaction solution. The temperature of the reaction solution at the time of the dropwise addition can usually be set to -120 ° C to 150 ° C, and preferably set to -90 ° C to 100 ° C. If the reaction temperature is too high, it may be difficult to control the reaction and it may be difficult to obtain reproducibility, and if it is too low, the production cost increases.

  In the method for producing a β-ferrandylene polymer, the reaction at a low temperature is advantageous in terms of increasing the degree of polymerization. For example, by reacting at −80 to 70 ° C., the number average molecular weight Mn is 100,000 or more. A β-ferrandylene polymer of about 140,000 can be easily obtained. Moreover, you may make it react at -15-40 degreeC, The beta ferrandylene polymer whose number average molecular weight Mn is about 50,000-100,000 can be obtained easily at this temperature.

  The reaction time of the cationic polymerization is not particularly limited, and may be appropriately adjusted so as to obtain a β-ferrandylene polymer having desired characteristics according to the conditions such as the type and amount of the polymerization catalyst, the reaction temperature, and the reaction equipment. it can. In general, a β-ferrandylene polymer having desired characteristics can be obtained by reacting for about 1 second to 100 hours, preferably about 10 seconds to 1 hour, more preferably about 30 seconds to 10 minutes.

  The β-ferrandol polymer used in the present invention may be a homopolymer of β-ferrandol, or a copolymer of β-ferrandol and one or more other copolymerizable monomers. May be.

  In order to terminate the reaction, a terminator may be added after the reaction for a predetermined time. As the terminator, alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol and t-butanol are preferably used. The amount of addition of the terminator is not strictly defined, but is usually 0.01 to 10 times the volume of the reaction solvent, preferably 0.1 to 1 times the volume.

  Examples of the method for separating the β-ferrandylene polymer obtained by polymerization in the reaction solution from the solvent include reprecipitation, evaporation of the solvent by heating, removal of the solvent by reduced pressure, and removal of the solvent by water vapor (coagulant). And other known methods such as removal of the deaerated solvent by an extruder can be applied.

  When it is necessary to neutralize and remove the chlorine-based Lewis acid catalyst when the polymer is separated from the solvent, a generally known neutralizing agent such as sodium hydroxide, sodium hydrogen carbonate, ammonia, etc. A neutralizing agent can be used and is not particularly limited. Furthermore, in applications where the requirements for transparency and thermal stability are severe, it is desired to sufficiently remove chlorine and neutralized salts remaining as impurities in the resulting polymer. The removal method is not particularly limited. For example, it is preferable to purify the polymer by a treatment such as water addition at the time of re-pillowing the polymer. In particular, in order to improve optical properties and electrical insulation, the content of residual neutralized salt is preferably 100 ppm or less with respect to the mass of the polymer. Especially preferably, it is 10 ppm or less.

<Β Ferrandylene Polymer>
The number average molecular weight Mn of the β-ferrandylene polymer obtained as described above is from the viewpoint of increasing the viscosity and melt viscosity of the polymerization solution, moldability, the strength of the formed durable transparent plate member, and heat resistance. 10,000 to 1,000,000 are preferable. The number average molecular weight Mn of the β-ferrandylene polymer used in the present invention can be adjusted to 20,000 to 500,000, 30,000 to 400,000, or 40,000 to 300,000. It can also be prepared, 50,000 to 250,000 can be prepared, 60,000 to 200,000 can be prepared, 70,000 to 150,000 can be prepared, 80,000 to 12 It can also be prepared in a million. If the molecular weight of the polymer is too large, the viscosity of the polymerization solution increases and the productivity of the polymer deteriorates, or the melt viscosity of the polymer increases and the moldability may deteriorate. On the other hand, if the molecular weight is too small, the strength of the durable transparent plate-like member obtained using the polymer is lowered, and the glass transition temperature is less than 80 ° C., so that sufficient heat resistance may not be exhibited.

  The glass transition temperature Tg of the β-ferrandylene polymer is preferably about 80 to 350 ° C., more preferably 85 to 250 ° C., from the viewpoint of increasing heat resistance, moldability, and the strength of the formed durable transparent plate member. 90-200 degreeC is still more preferable. The glass transition temperature Tg of the β-ferrandylene polymer used in the present invention can be adjusted to 80 ° C. or higher and 200 ° C. or lower, 85 ° C. or higher and 200 ° C. or lower, or 90 ° C. or higher and 200 ° C. or lower. It can be prepared at 95 ° C. or less, can be prepared at 95 ° C. or more and 200 ° C. or less, can be prepared at 100 ° C. or more and 200 ° C. or less, and can be prepared at 110 ° C. or more and 200 ° C. or less. In addition, it can be adjusted to 120 ° C. to 200 ° C., 125 ° C. to 200 ° C., and 130 ° C. to 200 ° C. When the glass transition temperature Tg is too high, the melt viscosity of the β-ferrandylene polymer becomes high and the moldability may be deteriorated. On the other hand, if the glass transition temperature Tg is too low, the heat resistant use temperature of the formed durable transparent plate member is lowered, which is not practical. Usually, the glass transition temperature Tg and heat resistance can be improved by increasing the molecular weight of the β-ferrandylene polymer and by hydrogenating the β-ferrandylene polymer.

In the present specification and claims, the number average molecular weight Mn of β-ferrandylene polymer is obtained according to the size exclusion chromatography method defined in JIS-K-0124-2002, and is a gel. It is obtained from the value of the differential refraction detector measured by permeation chromatography (GPC) and the calibration curve of standard polystyrene. The glass transition temperature Tg was measured according to the method defined in JIS-K-7121-1987 “Method for Measuring Plastic Transition Temperature”. More specifically, the glass transition temperature Tg (T _The temperature determined as _mg ) is the glass transition temperature Tg in the present specification and claims.

<Optical isomerism of β-ferrandrene>
The β-ferrandolene, which is a material of the β-ferrandylene polymer used in the present invention, is a mixture or a racemate of compounds that are optical isomers (enantiomers) represented by the following chemical formulas (I) and (II). Alternatively, only one of the optical isomers may be used. Chemically synthesized β-ferrandolene is usually a mixture or a racemate. When using β-ferrandolene consisting only of one of the optical isomers, it can be obtained by optical isomerization separation by using a method such as chromatography using a chiral column, diastereomer method using an optical resolving agent, etc. Materials may be used.

  The β-ferrandol polymer obtained by using the above-mentioned mixture or racemate of β-ferrandol as a material includes the following chemical formulas (I-1), (I-2), (II-1) and (II-2). Any one or more of monomer units (repeating units) represented by In each chemical formula, parentheses indicate a bond with an adjacent monomer unit that is polymerized (bonded).

  The β-ferrandylene polymer used in the present invention may have one, two, or three types of monomer units represented by the above chemical formulas. You may have, and you may have 4 types.

  In the β-ferrandylene polymer used in the present invention, when the mixture or racemate of the chemical formulas (I) and (II) is used as the material, the chemical formulas (I-1), (I-2), It is considered that β ferrandolene units represented by (II-1) and (II-2) are contained in a total of 50% by mass or more with respect to the total mass of the β ferrandolene polymer. The content is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, further preferably 80 to 100% by mass, and most preferably 90 to 100% by mass.

<Hydrogenation to β-ferrandylene polymer>
Hydrogenation (hydrogenation) can be performed on the olefinic carbon-carbon double bond of the β-ferrandylene polymer used in the present invention. By performing hydrogenation, a polymer having further improved heat resistance can be obtained.

  As a method of adding hydrogen to the β-ferrandylene polymer, a known method of adding hydrogen to a conventional polymer can be applied. As the hydrogenation catalyst used in this case, catalysts generally used for hydrogenation reactions of olefins and aromatic compounds can be applied. For example, transition metals such as palladium, platinum, nickel, rhodium, ruthenium and the like are used as carbon. , Supported metal catalyst supported on a carrier such as alumina, silica, diatomaceous earth; homogeneous catalyst composed of organic transition metal compounds such as titanium, cobalt, nickel and organometallic compounds such as lithium, magnesium, aluminum, tin; Examples thereof include metal complex catalysts such as rhodium and ruthenium.

  Examples of the supported metal catalyst include nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina, platinum / silica, platinum / alumina, rhodium / Examples of the catalyst include silica, rhodium / alumina, ruthenium / silica, and ruthenium / alumina.

  Examples of the homogeneous catalyst include acetic acid / cobalt triethylaluminum, nickel trioctylate / triisobutylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxy A combination of titanate and dimethylmagnesium can be mentioned.

  Examples of the metal complex catalyst include chlorotris (triphenylphosphine) rhodium, dihydridotetra (triphenylphosphine) ruthenium, hydrido (acetonitrile) tris (triphenylphosphine) ruthenium, carbonylchlorohydridotris (triphenylphosphine) ruthenium, Examples include carbonyl dihydridotris (triphenylphosphine) ruthenium.

Among the catalysts used in the hydrogenation reaction exemplified here, the supported metal catalyst is particularly preferable because it can be easily separated and recovered by filtration together with the polymerization catalyst after the hydrogenation reaction.
The said catalyst may be used individually by 1 type, and may use 2 or more types together.

  The reaction temperature at the time of hydrogenation can usually be carried out at -20 ° C to 250 ° C, preferably -10 ° C to 220 ° C, more preferably 0-200 ° C. If the reaction temperature is too high, the polymer may be thermally decomposed, and if it is too low, the reaction rate may be slow and the reaction may not be completed.

The hydrogen pressure at the time of hydrogenation can be usually 0.1-100 kgf / cm ² , preferably 0.5-70 kgf / cm ² , more preferably 1-50 kgf / cm ² . . If the hydrogen pressure is too low, the hydrogenation reaction is slow, and if it is too high, a high pressure reactor is required.

The solvent for the hydrogenation is not particularly limited as long as the polymer is dissolved and the catalyst is inert. From the viewpoint of the solubility and reactivity of the hydrogenated product of the polymer, examples include aliphatic hydrocarbons, halogenated hydrocarbons, and aromatic hydrocarbons. Specifically, aromatic hydrocarbon solvents such as benzene and toluene; aliphatic carbonization such as n-pentane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane and decalin Hydrogen solvents; ether solvents such as tetrahydrofuran and ethylene glycol dimethyl ether; methylene chloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, n-propyl chloride, 1-chloro-n-butane, 2-chloro-n -Halogenated hydrocarbon solvents such as butane. Of these organic solvents, hydrocarbon solvents are particularly preferable from the viewpoints of solubility and reactivity.
The said organic solvent may be used individually by 1 type, and may use 2 or more types together.

  In the hydrogenation, it is also possible to carry out the hydrogenation reaction as it is without exchanging the solvent of the reaction solution after the polymerization reaction of β-ferrandrene is completed. When hydrogenation is performed without replacing the solvent in this way, waste liquid discharged from the production process is reduced, which is preferable from the viewpoint of reducing the environmental load.

  The reaction time of the hydrogenation can be usually performed for about 0.1 to 20 hours. As a measure of completion of the hydrogenation reaction, for example, among the olefinic carbon-carbon double bonds (unsaturated bonds) of the polymer before hydrogenation, preferably 70% or more, more preferably 80% or more, It is desirable to continue the hydrogenation until preferably 90% or more, particularly preferably 95% or more is saturated, most preferably 100% is saturated. By sufficiently hydrogenating the β-ferrandylene polymer, a polymer excellent in chemical resistance, heat resistance and light resistance can be obtained.

As a method for obtaining the hydrogenation rate of the olefinic carbon-carbon double bond in the polymer before and after the hydrogenation, in general, iodine titration method, infrared spectroscopic measurement, nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum) A method of calculating from an analysis value such as measurement is known.

In the present specification and claims, the hydrogenation ratio of the β-ferrandylene polymer to the olefinic carbon-carbon double bond is a nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum) using deuterated chloroform as a solvent. It is calculated using the measured value. Specifically, the integrated value of the signal detected at δ = 5.0 to 6.0 ppm, that is, the integrated value of the signal derived from the proton of the olefinic carbon-carbon double bond, assuming that the proton of tetramethylsilane is 0 ppm. The ratio (A / B) between A and the integral value of the signal detected at 0.5 to 2.5 ppm, that is, the integral value B of the signal derived from the saturated hydrocarbon proton is calculated. This ratio decreases as the hydrogenation rate increases. By calculating the ratio before hydrogenation (A / B (before hydrogenation)) and the ratio after hydrogenation (A / B (after hydrogenation)), respectively, and substituting them into the following formula, hydrogenation The rate can be determined.

Hydrogenation rate (%) =
(Ratio (A / B (before hydrogenation))-ratio (A / B (after hydrogenation)) × 100 ÷ ratio (A / B (before hydrogenation))

The glass transition temperature Tg of the polymer obtained by hydrogenating the β-ferrandylene polymer is assumed to be used in an environment close to a heat source (for example, a light source that generates heat), or surface processing is easy. From the viewpoint of becoming, the higher one is preferable. The durable transparent plate member according to the present invention may be subjected to a known surface treatment (surface treatment) in order to improve its chemical resistance, impart antistatic properties, or impart electrical conductivity. it can. Since these surface treatments can be easily performed, the Tg of the hydrogenated β-ferrandylene polymer is preferably 120 ° C. or higher. When Tg exceeds about 200 ° C., the melt viscosity of the β-ferrandylene polymer increases, and the moldability may be deteriorated. On the other hand, when the Tg is less than 80 ° C., the heat resistant use temperature of the durable transparent plate-like member is lowered, which is not preferable.
The method for measuring the glass transition temperature Tg of the hydrogenated β-ferrandylene polymer may be the same as the method for measuring the glass transition temperature Tg of the non-hydrogenated β-ferrandylene polymer.

The total light transmittance of the β-ferrandylene polymer used in the present invention is preferably as high as the properties usually required for its use, preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. . For example, when a flat test piece having a thickness of about 3.2 mm made only of β-ferrandrene polymer is measured, the total light transmittance is preferably 80% or more, more preferably 85% or more. 90% or more is more preferable, and 95% or more is most preferable.
Here, the total light transmittance is a value measured in accordance with JIS-K-7361: 1997 (ISO13468-1: 1996).

The β-ferrandylene polymer used in the present invention preferably has a low water absorption rate from the viewpoint of dimensional stability. The water absorption of the β-ferrandylene polymer is 0.2 when the mass change of the test piece when the test piece is placed in an atmosphere of 60 ° C. and 90% RH (relative humidity) for 24 hours is measured as the saturated water absorption. % Or less is preferable, 0.1% or less is more preferable, and 0.05% or less is more preferable.
Here, the water absorption is a numerical value measured according to JIS-K-7209: 2000. In this case, as an example of the test piece, a product obtained by molding the β-ferrandylene polymer into a flat plate having a thickness of about 3.2 mm can be used.

Since the specific gravity of the β-ferrandylene polymer used in the present invention is small, a light durable transparent plate-like member can be obtained. The specific gravity of the β-ferrandylene polymer used in the present invention is 0.85 or more and less than 1.0, preferably 0.85 to 0.98.
It is usually difficult to obtain a β-ferrandylene polymer having a specific gravity of less than 0.85. Further, if the specific gravity is 1.0 or more, the object of weight reduction cannot be sufficiently achieved.
Here, the specific gravity is a numerical value measured according to A method of JIS-K-7112: 1999.

  In general, when the photoelastic coefficient of the resin constituting the molded article is large at a temperature equal to or higher than Tg, there is a problem that the optical distortion of the obtained molded article increases. Therefore, when trying to obtain a molded product with a small optical distortion, the range in which the molding conditions can be selected becomes narrow, and there is a problem that productivity is lowered.

  Accordingly, it is preferable that the β-ferrandylene polymer used in the present invention has a small photoelastic coefficient, and it is more preferable that the photoelastic coefficient is small even at a temperature equal to or higher than the glass transition temperature Tg. By using a β-ferrandylene polymer having low photoelasticity, a durable transparent plate-like member with little optical distortion can be obtained.

A suitable photoelastic coefficient at a temperature equal to or higher than Tg (for example, Tg + 20 ° C.) of the β-ferrandylene polymer to be used cannot be generally specified depending on the use, but is −3.0 × 10 ^{−10 to} 3.0 × 10 ⁻¹⁰ cm ² / dyn is preferable, and −1.0 × 10 ^{−10 to} 1.0 × 10 ⁻¹⁰ cm ² / dyn is more preferable. By having a photoelastic coefficient in this range, it is possible to obtain a durable transparent plate-like member with small optical distortion with high productivity. Note that 1 dyn = 10 ⁻⁵ N.

  The bending elastic modulus of the β-ferrandylene polymer used in the present invention is preferably 2500 MPa or more, and more preferably 2700 MPa or more. When the bending elastic modulus is within this range, deformation due to bending can be suppressed, and the thickness of the durable transparent plate-like member can be reduced. Here, the flexural modulus is a numerical value measured by a method based on ASTM D790. At this time, as the test piece, a product obtained by molding the β-ferrandylene polymer into, for example, a flat test piece shape having a thickness of about 3.2 mm can be used.

When the β-ferrandylene polymer used in the present invention is formed into a plate having a thickness of 3.2 mm, the tensile strength of the plate-like sample is preferably 60 MPa or more, more preferably 70 MPa or more, and further preferably 80 MPa or more. The upper limit of the tensile strength is not particularly limited, and the higher the strength, the better. However, the upper limit is usually about 100 MPa.
Here, the said tensile strength is a numerical value calculated | required by the measuring method based on ASTM D638.

<Durable transparent plate member>
The durable transparent plate-like member of the present invention is a durable transparent plate-like member in which the above-described β-ferrandylene polymer is contained in an amount of 50 to 100% by mass with respect to the total mass of the durable transparent plate-like member. .
The β-ferrandylene polymer constituting the durable transparent plate member has a specific gravity of 0.85 or more and less than 1.0, and a glass transition temperature of 100 ° C. or more.

  The content of the β-ferrandylene polymer contained in the durable transparent plate member of the present invention may be 60 to 100% by mass with respect to the total mass of the durable transparent plate member, or 70 To 100% by mass, 80 to 100% by mass, 90 to 100% by mass, 95 to 100% by mass, or 98 to 100% It may be mass%.

  In order to improve the mechanical strength and heat resistance of the durable transparent plate-like member of the present invention, the mechanical strength and heat resistance of the β-ferrandylene polymer which is the main component of the durable transparent plate-like member are improved. Just do it. From the viewpoint of improving the mechanical strength and heat resistance of the β-ferrandylene polymer, the preferred Tg is preferably 100 to 350 ° C, more preferably 100 to 250 ° C, and still more preferably 100 to 200 ° C. From the same viewpoint, the preferred number average molecular weight Mn of the β-ferrandylene polymer is preferably as large as possible, preferably 60,000 or more, preferably 80,000 or more, more preferably 100,000 or more, and further preferably 120,000 or more, 140,000 or more is even more preferable, 160,000 or more is particularly preferable, and 180,000 or more is most preferable. The upper limit of the number average molecular weight Mn is not particularly limited, but is usually preferably 800,000 or less, more preferably 600,000 or less, and still more preferably 400,000 or less, from the viewpoint of improving moldability and workability.

Further, from the same viewpoint as described above, the preferred weight average molecular weight Mw of the β-ferrandylene polymer is preferably as large as possible, preferably 50,000 or more, more preferably 70,000 or more, still more preferably 90,000 or more, and 110,000 or more. Even more preferred is 130,000 or more, most preferred is 150,000 or more. The upper limit of the weight average molecular weight Mw is not particularly limited, but is usually preferably 1 million or less, more preferably 800,000 or less, and still more preferably 600,000 or less from the viewpoint of improving moldability and workability. The weight average molecular weight can be calculated from measurement data obtained by the same method as the number average molecular weight.
From the same viewpoint as described above, the Mw / Mn of the β-ferrandylene polymer is preferably 1 to 25, more preferably 1.05 to 20, and still more preferably 1.1 to 10.

  The specific gravity of the durable transparent plate member of the present invention is usually 0.85 to 1.0 when the β-ferrandylene polymer constitutes 50 to 100% by mass of the total mass of the plate member. Can be in the range. Since the β-ferrandylene polymer has a lighter specific gravity than conventional acrylic resins, PET resins, polyvinyl chloride resins, etc., the durable transparent plate-like member according to the present invention having the β-ferrandylene polymer as a main component is It is superior in light weight than the transparent plate-shaped member made of these conventional resins.

  From the viewpoint of improving the heat resistance of the durable transparent plate-like member of the present invention, at least a part of the olefinic carbon-carbon double bond of the β-ferrandylene polymer used in the present invention is hydrogenated. Is preferred.

The total light transmittance of the durable transparent plate-like member of the present invention is preferably as high as the properties usually required for its use, preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. For example, when a flat test piece having a thickness of about 3.2 mm is measured as an example of the durable transparent plate member of the present invention, the total light transmittance is preferably 80% or more, and 85% or more. More preferably, it is more preferably 90% or more, and most preferably 95% or more.
Here, the total light transmittance is a value measured in accordance with JIS-K-7361: 1997 (ISO13468-1: 1996).

The water absorption of the durable transparent plate-like member of the present invention is 60 ° C. and 90% when the β-ferrandylene polymer described above constitutes 70 to 100% by mass of the total mass of the durable transparent plate-like member. When the mass change when the durable transparent plate-like member is placed in an RH (relative humidity) atmosphere for 24 hours is measured as a saturated water absorption, it is preferably 0.2% or less, more preferably 0.1% or less. 0.05% or less is more preferable. Here, the water absorption is a numerical value measured according to JIS-K-7209: 2000.
Since the β-ferrandylene polymer has a lower water absorption than the conventional acrylic resin, the durable transparent plate-like member of the present invention having the β-ferrandylene polymer as a main component is a plate-like material made of a conventional acrylic resin. Dimensional stability is superior to members.

  The photoelastic coefficient of the durable transparent plate-like member of the present invention is such that when the β-ferrandylene polymer mentioned above constitutes 95 to 100% by mass of the total mass of the durable transparent plate-like member, It can be equivalent to a suitable photoelastic coefficient of the drain polymer.

  The bending elastic modulus of the durable transparent plate-like member of the present invention is such that the above-described β-ferrandene polymer constitutes 95 to 100% by mass of the total mass of the durable transparent plate-like member. It can be made equal to the preferred flexural modulus of the drain polymer.

  In the β-ferrandylene polymer for forming the durable transparent plate-like member of the present invention, various known compounding agents may be used alone or as required, as long as the object of the present invention is not impaired. You may combine and mix a seed or more.

  The compounding agent is not particularly limited as long as it is usually used in the conventional resin industry. For example, an antioxidant, an ultraviolet absorber, a light stabilizer, a near infrared absorber, a colorant such as a dye or a pigment. , Lubricants, plasticizers (softening agents), antistatic agents, fluorescent brighteners, fillers and the like.

  Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. Among these antioxidants, phenolic antioxidants are preferable, and alkyl-substituted phenolic antioxidants are particularly preferable.

  Examples of the phenolic antioxidant include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t- Acrylate compounds such as amyl-6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate; octadecyl-3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionate, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis (methylene-3- (3 ′, 5′-di-) -Butyl-4'-hydroxyphenylpropionate) methane [i.e. pentaerythrimethyl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenylpropionate)], triethylene glycol bis (3- Alkyl-substituted phenolic compounds such as (3-t-butyl-4-hydroxy-5-methylphenyl) propionate); 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bisoctyl Thio-1,3,5-triazine, 4-bisoctylthio-1,3,5-triazine, 2-octylthio-4,6-bis- (3,5-di-t-butyl-4-oxyanilino)- Examples include triazine group-containing phenol compounds such as 1,3,5-triazine.

  Examples of the phosphorus antioxidant include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4- Di-t-butylphenyl) phosphite, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc. Monophosphite compounds; 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecylphosphite), 4,4′-isopropylidene-bis (phenyl-di-alkyl ( And diphosphite compounds such as C12 to C15) phosphite). Among these, monophosphite compounds are preferable, and tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite and the like are particularly preferable.

  Examples of the sulfur antioxidant include dilauryl 3,3-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3-thio. Dipropionate, pentaerythritol-tetrakis- (β-lauryl-thiopropionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane Etc.

  The said antioxidant can be used individually or in combination of 2 or more types, respectively. The blending amount of the antioxidant may be appropriately determined as long as the object of the present invention is not impaired, for example, about 0.001 to 5 parts by weight with respect to 100 parts by weight of the β-ferrandylene polymer, Preferably it can be used in the range of 0.01 to 1 part by weight.

  Examples of the ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) 2H-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H. -Benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -2H-benzotriazole, 5-chloro-2- (3,5-di-t-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-t-amyl-2-hydroxy Benzotriazole ultraviolet absorbers such as phenyl) -2H-benzotriazole; 4-t-butylphenyl-2-hydroxybenzoate, phenyl-2-hydroxybenzoate Zoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (2H- Benzotriazol-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole Benzoate ultraviolet absorbers such as 2- (2-hydroxy-4-octylphenyl) -2H-benzotriazole; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone -5-sulfonic acid trihydrate, 2-hydroxy-4-octyloxybenzophenone, 4- Benzophenone ultraviolet rays such as decyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone Absorber; acrylate ultraviolet absorber such as ethyl-2-cyano-3,3-diphenyl acrylate, 2′-ethylhexyl-2-cyano-3,3-diphenyl acrylate; [2,2′-thiobis (4-t -Octylphenolate)] A metal complex ultraviolet absorber such as 2-ethylhexylamine nickel can be used.

  Examples of the light stabilizer include 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, and bis (1,2, 2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 4- (3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionyloxy) -1- (2- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) ethyl) -2,2,6 And hindered amine light stabilizers such as 1,6-tetramethylpiperidine.

  Examples of the near-infrared absorber include cyanine-based near-infrared absorbers; pyrylium-based near-infrared absorbers; squarylium-based near-infrared absorbers; croconium-based near-infrared absorbers; Dithiol metal complex near infrared absorbers; naphthoquinone near infrared absorbers; anthraquinone near infrared absorbers; indophenol near infrared absorbers; As commercially available near infrared absorbers, SIR-103, SIR-114, SIR-128, SIR-130, SIR-132, SIR-152, SIR-159, SIR-162 (above, Mitsui Toatsu Dye Co., Ltd.) Company-made), Kayasorb IR-750, Kayasorb IRG-002, Kayasorb IRG-003, Kayasorb IR-820B, Kayasorb IRG-022, Kayasorb IRG-023, Kayasorb CY-2, Kayasorb CY-2 , Manufactured by Nippon Kayaku Co., Ltd.).

  The dye is not particularly limited as long as it is uniformly dispersed or dissolved in the β-ferrandylene polymer to be used. For example, an oil-soluble dye (various C.I. Solvent dyes). Specific examples of the oil-soluble dye include, for example, “Color Index” published by The Society of Dyers and Colorists, Vol. 3. Various C.I. I. Solvent dyes may be mentioned.

  Among the pigments, organic pigments include, for example, diarylide pigments such as Pigment Red 38; azo lake pigments such as Pigment Red 48: 2, Pigment Red 53, and Pigment Red 57: 1; Pigment Red 144 and Pigment Red 166. Pigment Red 220, Pigment Red 221 and Pigment Red 248; condensed azo pigments such as Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185 and Pigment Red 208; Pigment Red 122 and the like Quinacridone pigments; perylene pigments such as Pigment Red 149, Pigment Red 178, and Pigment Red 179; and anthraquinone pigments such as Pigment Red 177. Examples of inorganic pigments include titanium oxide, carbon black, red pepper, chrome red, molybdenum red, resurge, and iron oxide.

  When the durable transparent plate-like member of the present invention needs to be colored, any of the dyes and pigments can be used within the scope of the object of the present invention. For example, in applications that require consideration of micro optical properties, coloring with dyes is preferred. In addition, the ultraviolet absorber may visually show a yellow to red color, and the near-infrared absorber may visually show a black color. Therefore, these light absorbers and the dyes and pigments are strictly used. There is no need to distinguish between them. Moreover, you may use combining these light absorption materials, the said dye, and a pigment.

Examples of the lubricant include organic compounds such as aliphatic alcohol esters, polyhydric alcohol esters, and partial esters, and inorganic fine particles.
Examples of the organic compound include glycerol monostearate, glycerol monolaurate, glycerol distearate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and the like.
Examples of the inorganic fine particles include oxides, sulfides, hydroxides, nitrides, halides, carbonates, sulfates, acetates of Group 1, Group 2, Group 4, and Group 6-14 elements of the Periodic Table. Examples thereof include fine particles such as phosphates, phosphites, organic carboxylates, silicates, titanates, borates, and hydrates thereof, complex compounds centered on them, and natural compounds.

  Examples of the plasticizer include tricresyl phosphate, trixylenyl phosphate, triphenyl phosphate, triethylphenyl phosphate, diphenyl cresyl phosphate, monophenyl dicresyl phosphate, diphenyl monoxylenyl phosphate Phosphoric acid triester plasticizers such as monophenyldixylenyl phosphate, tributyl phosphate, triethyl phosphate; dimethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di-2 phthalate -Phthalic acid ester plasticizers such as ethylhexyl, diisononyl phthalate, octyldecyl phthalate, and butylbenzyl phthalate; fatty acid monobasic acid esters such as butyl oleate and glycerol monooleate System plasticizers; dihydric alcohol ester-based plasticizers; oxy ester plasticizer and the like. Among these, phosphate triester plasticizers are preferable, and tricresyl phosphate and trixylenyl phosphate are particularly preferable.

  Other specific examples of the plasticizer include squalane (C30H62, Mw = 422.8), liquid paraffin (white oil, ISO VG10, ISO VG15, ISO VG32, ISO VG68, ISO VG100 as defined in JIS-K-2231. ISO VG8 and ISO VG21), polyisobutene, hydrogenated polybutadiene, hydrogenated polyisoprene and the like. Among these, squalane, liquid paraffin, and polyisobutene are preferable.

  Examples of the antistatic agent include long-chain alkyl alcohols such as stearyl alcohol and behenyl alcohol, fatty acid esters of polyhydric alcohols such as glycerin monostearate and pentaerythritol monostearate, and stearyl alcohol and behenyl alcohol are particularly preferable.

  The said compounding agent can be used individually or in mixture of 2 or more types. The mixing ratio is appropriately selected as long as the object of the present invention is not impaired. The amount of each compounding agent is appropriately selected within a range that does not impair the object of the present invention. The amount of each compounding agent is usually 0. It is preferable to use in the range of about 001 to 5 parts by weight, preferably 0.01 to 1 part by weight.

  The β-ferrandylene polymer for forming the durable transparent plate-like member according to the present invention can be blended with other polymer components as needed within a range not impairing the object of the present invention. Examples of the other polymer include rubbery polymers, specifically, diene rubbers such as natural rubber, polybutadiene rubber, polyisoprene rubber, acrylonitrile / butadiene copolymer rubber; and styrene / butadiene copolymer. Rubber, styrene / isoprene copolymer rubber, styrene / butadiene / isoprene terpolymer rubber; hydrogenated diene rubber; ethylene / α-olefin copolymer such as ethylene / propylene copolymer, propylene / other Saturated polyolefin rubbers such as α-olefin copolymers; α-olefins such as ethylene / propylene / diene copolymers, α-olefin / diene copolymers, isobutylene / isoprene copolymers, and isobutylene / diene copolymers・ Diene polymer rubber; urethane rubber, silicone rubber, polyester Special rubbers such as tellurium rubber, acrylic rubber, propylene oxide rubber and ethylene / acrylic rubber; thermoplastic elastomers such as styrene / butadiene / styrene block copolymer rubber and styrene / isoprene / styrene block copolymer rubber; heat of hydrogenation Mention may be made of plastic elastomers; urethane thermoplastic elastomers; polyamide thermoplastic elastomers; 1,2-polybutadiene thermoplastic elastomers. The blending amount is appropriately selected within a range not impairing the object of the present invention, and is, for example, about 3 to 30 parts by weight, preferably 5 to 100 parts by weight of the β-ferrandylene polymer. It is preferably used in the range of 20 parts by weight.

  The durable transparent plate-like member of the present invention is a transparent durable plate-like member formed with the aforementioned β-ferrandrene polymer as a main component. Here, durability refers to having sufficient impact resistance, weather resistance, light resistance, etc., in order to protect a target object such as a vehicle or a human from the external environment. Moreover, the durable transparent plate-shaped member of the present invention is a member having such a size that a partition can be formed in the space between the object and the external environment. As the external environment, for example, dust, dust, visible light, invisible light, rain, snow, acid, alkali, other chemicals, physical impact, etc. are applied to the installed durable transparent plate-like member. The environment that can affect

  As a method for protecting an object from the external environment using the durable transparent plate-like member of the present invention, for example, by installing the durable transparent plate-like member at a specific distance from the protected object, rain, wind, There is a method for protecting an object from external factors from a certain direction such as light rays. Further, a method of surrounding the object to be protected with a durable transparent plate member can also be adopted. Moreover, the use which covers a part or all of the space (for example, experiment chamber) which handles an acid, an alkali, another chemical | medical agent, etc. with a durable transparent plate-like member using the advantage which is transparent is also mentioned. In such an application, since the member is transparent, the internal state can be observed from the outside.

  The size (vertical length and horizontal length) of the durable transparent plate member of the present invention is not particularly limited, and may be, for example, a size of 50 mm or more, or a size of 100 mm or more, The size may be 300 mm or more, or may be 500 mm or more.

  The thickness of the durable transparent plate-like member of the present invention is appropriately selected according to the purpose of use, but in order to sufficiently exhibit the protective function, a range of 0.5 mm to 500 mm is preferable, and 1.0 mm The range of -300 mm is more preferable, and the range of 3.0 mm-100 mm is still more preferable. When the thickness is within these preferable ranges, excellent characteristics such as mechanical strength, weather resistance, light resistance, and light transmittance can be greatly exhibited.

  The shape of the surface (the shape seen in the thickness direction) of the durable transparent plate-like member of the present invention is not particularly limited, and for example, a shape such as a quadrangle, a circle, an ellipse, other polygons, or a similar shape is available. Can be mentioned. In the case of a polygon including a quadrangle, the ratio (Y / X) of the thickness (X) of the plate and the length (Y) of the shortest side constituting the polygon is 2.0 or more, preferably When it is 3.0 or more, and more preferably 5.0 or more, excellent characteristics such as mechanical strength, weather resistance, light resistance, and light transmittance of the durable transparent plate member can be exhibited.

  The durable transparent plate-like member of the present invention has a high balance of mechanical strength, chemical resistance, weather resistance, light resistance and light transmission, so that it is a plate material having a protective or protective function, for outdoor use. Suitable for applications such as large transparent plates. Specifically, roofs for car (vehicle) storage such as carports and garages; windows and partitions for residential exteriors and glazings (sunrooms, balconies, terraces, etc.); windows for vending machines; showcases, showrooms Windows for vehicles such as sunroofs, lift hoods, gondola windows, ropeway windows and the like.

  The durable transparent plate-like member of the present invention is required for impact resistance such as mechanical strength, and is suitable for applications requiring weather resistance and light resistance as required. As the size of the plate-like member when used in these applications, for example, when used for carports, windows, glazings, etc., the present invention is used when it is 300 mm square or more, preferably 500 mm square or more. The characteristic which it has can be exhibited largely. Further, for example, when used for a residential exterior or the like, it is also possible to use a combination of a plurality of the plate-like members of about 50 to 100 mm square. Furthermore, the durable transparent plate-like member of the present invention is useful for applications requiring weather resistance, light resistance, and chemical resistance, such as signs, bulletin boards, and highway signs.

<Method for producing durable transparent plate-like member>
The method for producing (molding) the durable transparent plate member according to the present invention is not particularly limited, and a known method for producing a conventional plate member made of transparent resin, for example, a melt molding method can be applied. Examples of the melt molding method include known molding methods such as a method using a T die, a melt extrusion method such as an inflation method, a calendar method, a hot press method, and an injection molding method. Among these molding methods, a melt extrusion method using a T die that can reduce thickness unevenness is preferable. The conditions of the melt molding method are appropriately designed according to the shape and size of the member to be manufactured. For example, in the melt molding method using a T die, the resin temperature is appropriately selected in the range of the glass transition temperature to the decomposition temperature. As an example, the resin temperature at the time of melting can be set in the range of about 100 to 400 ° C., preferably 150 to 350 ° C., more preferably 200 to 300 ° C. Under the present circumstances, the temperature of a take-up roll can be made into the range of about 0-200 degreeC, Preferably it is 30-180 degreeC, More preferably, it is 50-150 degreeC.

The durable transparent plate-like member of the present invention is a polyolefin resin, acrylic resin, carbonate resin, etc. with respect to chemical resistance, light transmittance, heat resistance, water absorption, light resistance, photoelastic coefficient, mechanical strength, etc. Compared to conventional petroleum-derived resins, it has the same or better physical properties. In addition, since the specific gravity is lighter than many conventional resins, it is excellent in lightness.
Further, the transparent plate-like member made of a conventionally known β-pinene polymer has excellent lightness equivalent to that of the durable transparent plate-like member of the present invention, but in the mechanical strength such as tensile strength of the present invention. A durable transparent plate-like member made of β-ferrandylene polymer is superior. As one of the factors, it can be considered that β-ferrandylene tends to form a polymer having a large number average molecular weight and easily forms a transparent plate-like member having excellent mechanical strength.
Therefore, by using the aforementioned β-ferrandylene polymer, a thin and lightweight durable transparent plate-like member having the same strength can be produced.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited by these examples.

[Synthesis Example 1]
As a material for the durable transparent plate member according to the present invention, a hydrogenated product of β-ferrandylene polymer was synthesized as follows.
[Production of β-ferrandylene polymer]
In a dried glass flask, 68 parts by weight of hexane (manufactured by Kanto Chemical Co., Inc.) was added and cooled to 0 ° C. A Lewis acid catalyst EtAlCl ₂ (ethylaluminum dichloride) (17% hexane solution, about 1 mol / L, manufactured by Tokyo Chemical Industry Co., Ltd.), 0.37 parts by weight, was dispersed well and obtained by chemical synthesis. Then, 5.1 parts by weight of β-ferrandolene (purity 83.3%) was slowly added dropwise. After 1 minute, 8 parts by weight of methanol was added to stop the polymerization reaction. After the reaction solution was transferred to a separatory funnel, 20 parts by weight of 1% sodium hydroxide solution was added and stirred well, and then the aqueous phase was separated and removed. Next, the organic solvent phase was slowly evaporated by an evaporator, and the reaction solution was concentrated. About 40 parts by weight of the concentrated reaction solution was slowly added dropwise to 240 parts by weight of methanol to reprecipitate the polymer. The resulting precipitate was separated from the solution by filtration and sufficiently dried to obtain a β-ferrandylene polymer. The reaction rate of the monomer during the reaction was 100%.

  The obtained β-ferrandylene polymer had a number average molecular weight of 105,300 and a glass transition temperature of 85 ° C.

[Hydrogenation]
In a pressure vessel sufficiently purged with nitrogen, 61 parts by weight of dehydrated hexane and 4 parts by weight of the obtained β-ferrandrene polymer were charged and sufficiently dissolved. Next, 10 parts by weight of a palladium / alumina catalyst (Pd: 5%, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and a hydrogenation reaction was performed at 120 ° C. for 10 hours in an 8 MPa hydrogen atmosphere. The reaction solution is filtered using a filter made of Teflon (registered trademark) with a pore size of 1 μm, and after removing the catalyst, it is reprecipitated with methanol, the precipitate is sufficiently dried, and a hydrogenated product of β-ferrandylene polymer 4.5 parts by weight were obtained.

The hydrogenation proportion of the resulting β-phellandrene polymer was calculated by ^{1 H-NMR} spectrum measurement, it was 99.9%. The number average molecular weight of the polymer was 104,000, the glass transition temperature was 130 ° C., and the specific gravity was 0.93.

[Synthesis Example 2]
By the method of Synthesis Example 1, the reaction temperature was changed to −78 ° C. to prepare a β-ferrandylene polymer having a number average molecular weight of 139,400. Further hydrogenation was performed to prepare a hydrogenated β-ferrandylene polymer having a hydrogenation rate of 99.9%, a molecular weight of 138,500, a glass transition temperature of 139 ° C., and a specific gravity of 0.93.

(Reaction yield)
By the method using o-dichlorobenzene as an internal standard, it was calculated from the reduction rate of the signal area of the signal of 5.5 to 6.5 ppm derived from the conjugated double bond of β-ferrandolene monomer.

(Number average molecular weight)
It was measured in terms of standard polystyrene. As the apparatus, an LC-20AD liquid feeding unit manufactured by Shimadzu Corporation and a RID-10 differential refractive index detector were used. Two columns, Shodex KF803, manufactured by Showa Denko KK were used. As the solvent, THF (40 ° C.) was used.

(Hydrogen addition rate)
Deuterated chloroform was used as the solvent. A 0 ppm correction was made with TMS. The H-NMR spectrum was measured using an NMR device manufactured by JEOL Ltd., JNM-ECX400 (400 MHz). The measurement was performed at room temperature.
The reduction rate of the peak of 5.0 to 6.0 ppm due to the unsaturated bond in the spectrum before hydrogenation was determined. At this time, the ratio A / B of the integral value A of the signal derived from the proton of the olefinic double bond of 5.0 to 6.0 ppm and the integral value B of the signal derived from the proton of the saturated hydrocarbon of 0.5 to 2.5 ppm is Using. The hydrogenation rate (%) was calculated by (A / B (Before) −A / B (After)) × 100 / A / B (Before).

(Total light transmittance)
By a melt extrusion method, a 3.2 mm thick test piece made of the hydrogenated β-ferrandrene polymer prepared above was molded, and this was used as a measurement sample to measure the total light transmittance.
The total light transmittance was measured according to JIS-K-7361: 1997 (ISO13468-1: 1996). As a measuring device, a haze meter TC-H3DPK / II manufactured by Tokyo Denshoku Co., Ltd. was used.

(Glass-transition temperature)
According to JIS-K-7121-1987 “Plastic Transition Temperature Measuring Method”, the glass transition temperature Tg of the hydrogenated β-ferrandylene polymer prepared above was measured using a differential calorimeter. As the apparatus, DSC-60 manufactured by Shimadzu Corporation was used.

(Water absorption rate)
A plate having a length of 140 mm, a width of 60 mm, and a thickness of 0.8 mm was press-molded using the β-ferrandylene polymer hydrogenated product prepared above. This plate was placed in an atmosphere of 60 ° C. and 90% RH for 10 days, the ratio of the mass increased from the initial mass was calculated by the following formula, and the water absorption rate was determined.
Water absorption rate (%) = increase in mass x 100 / initial mass

(Light resistance)
By a melt extrusion method, a 0.5 mm thick test piece made of the hydrogenated β-ferrandrene polymer prepared above was molded, and the light resistance was evaluated using this as a measurement sample.
The test piece was placed in an ultraviolet exposure test apparatus and subjected to an accelerated exposure test for 100 hours, and the yellowing degree (ΔYI) before and after the YI (yellow index) test was measured. YI was measured according to JIS-K-7103 and evaluated according to the following criteria.
ΔYI = (YI after 100 hours of UV exposure) − (YI before UV exposure)
A: ΔYI ≦ 1 ... Long-term light resistance is very good
B: 1 <ΔYI: long-term light resistance is poor

(Photoelastic coefficient)
By a melt extrusion method, a 3.2 mm-thick test piece made of the hydrogenated β-ferrandrene polymer prepared above was molded, and the photoelastic coefficient was evaluated using this as a measurement sample.
The test piece was annealed at a temperature 20 ° C. lower than Tg overnight, and then a tensile stress was applied in the major axis direction at a temperature 20 ° C. higher than Tg. The retardation at that time was measured using an ellipsometer M220 (Japan) The photoelastic coefficient was calculated from the amount of change in retardation with respect to stress. The calculated changes were classified according to the following criteria.
A: Less than 1000: The amount of change is small and very good.
B: 1000 or more and less than 3000: The amount of change is within an allowable range, which is good.
C: 3000 or more: The amount of change is large and it is defective.
The unit of change is [× 10 ⁻¹³ cm ² / dyn].

(Flexural modulus)
In accordance with ASTM D790, the flexural modulus of each sample was measured. The results were judged according to the following criteria. The thickness of the sample was 3.2 mm.
A: 2500 MPa or more: Good
B: Less than 2500 MPa ... poor

(Tensile strength)
By a melt extrusion method, a 3.2 mm-thick test piece made of the hydrogenated β-ferrandrene polymer prepared above was molded, and this was used as a measurement sample to evaluate the tensile strength.
In accordance with ASTM D638, the tensile strength was measured at 23 ° C. using an autograph (manufactured by Shimadzu Corporation) and evaluated according to the following criteria.
A: 60 MPa or more: Strong tensile strength and good.
B: Less than 60 MPa ... It has a weak tensile strength and is defective.

(chemical resistance)
A 3.2 mm-thick test piece made of the hydrogenated β-ferrandrene polymer prepared above was molded by melt extrusion, and this was used as a measurement sample to evaluate chemical resistance as follows.
The test pieces were individually immersed in a pH 9 sodium carbonate aqueous solution, pH 4 hydrochloric acid, and ethanol solvent for 48 hours, and then the appearance of each test piece was observed and judged according to the following criteria.
A: The appearance was not changed in any solvent, and the turbidity and the total light transmittance were not changed.
B: Appearance changed with any of the solvents, and turbidity or total light transmittance decreased.

(specific gravity)
The specific gravity of a durable transparent plate-like member produced by the method described later was measured in accordance with Method A of JIS-K-7112: 1999 and evaluated according to the following criteria.
A: Specific gravity <1.0 ... Specific gravity is light and good.
B: 1.0 ≦ specific gravity <1.1 ... The specific gravity is heavy and it is defective.
C: 1.1 ≦ specific gravity: The specific gravity is heavier and poor.

(Moisture resistance)
About the durable transparent plate-shaped member produced by the method to be described later, a durability test for 1000 hours was performed under conditions of 80 ° C. and 90% RH, and the appearance change was visually observed. Judgment was made according to the following criteria.
A: There was no visual change and a good appearance was maintained.
B: White turbidity or deformation was observed, and the appearance was deteriorated.

(Water absorption rate)
The durable transparent plate-like member produced by the method described later was placed in an atmosphere of 60 ° C. and 90% RH for 10 days, and the ratio of the increased mass from the initial mass was calculated by the following formula to obtain the water absorption rate. .
Water absorption rate (%) = increase in mass x 100 / initial mass

<Manufacture of durable transparent plate member>
[Example 1]
A hydrogenated benzotriazole polymer obtained in Synthesis Example 1 (hereinafter sometimes referred to as a hydrogenated β-ferrandolene polymer) 100 parts by weight is a benzotriazole-based UV absorber as an UV absorber. 0.1 parts by weight of TINVIN P326 (manufactured by BASF), 0.1 part by weight of CHIMASSORB 944 FDL (manufactured by BASF) as a light stabilizer and hindered phenolic antioxidant IRGANOX 1010 (manufactured by BASF) as an antioxidant ) Mixing composition containing 0.1 parts by weight of powder blender, melt kneaded using a twin screw extruder (TEX33, manufactured by Nippon Steel), and containing pelletized β-ferrandylene polymer hydrogenated product I got a thing.
The obtained pellets of the mixed composition were dried with a hot air dryer at 90 ° C. for 5 hours. The dried pellets were melt extruded at 240 ° C. using a twin screw extruder equipped with a T die having a slit width of 10 cm to produce a durable transparent plate member having a thickness of about 3 mm. The evaluation results are shown in the following table.

[Example 2]
A durable transparent plate-like member having a thickness of about 3 mm was produced in the same manner as in Example 1 using the hydrogenated β-ferrandylene polymer obtained in Synthesis Example 2 as a material. The evaluation results are shown in the following table.

[Comparative Example 1]
The pellets of the alicyclic polyolefin resin (ZEONOR 1060R manufactured by Nippon Zeon Co., Ltd., glass transition temperature: 102 ° C.) were dried at 80 ° C. for 4 hours using a hot air dryer. Next, a pellet-shaped mixed assemblage was prepared in the same manner as in Example 1, and then the dried pellet of the mixed composition was melt extruded at 260 ° C. to form a durable transparent plate member. Each physical property of the produced durable transparent plate member was measured in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 2]
The pellets of polymethyl methacrylate resin (Acrypet TF-8, manufactured by Mitsubishi Rayon Co., Ltd.) were dried at 85 ° C. for 6 hours using a hot cloth drier. Next, using the same apparatus as in Example 1, the dried pellets were melt extruded at 220 ° C. to form a durable transparent plate member. Each physical property of the produced durable transparent plate member was measured in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 3]
Polycarbonate resin (Mitsubishi Engineering Plastics, Iupilon H-3000)
Was extruded at 280 ° C. to form a durable transparent plate member. Each physical property of the produced durable transparent plate member was measured in the same manner as in Example 1. The evaluation results are shown in Table 1.

  From the above results, the durable transparent plate-like members of Examples 1 and 2 are members having high light transmittance, heat resistance, light resistance, chemical resistance and tensile strength, low water absorption, and excellent lightness. It is clear that there is. It is understood that the durable transparent plate-like member of Example 1 has an excellent balance of physical properties as compared with the transparent plate-like members of Comparative Examples 1 to 3, and is advantageous in the use of the durable transparent plate-like member. Is done.

  The configurations and combinations thereof in the embodiments described above are examples, and the addition, omission, replacement, and other modifications of the configurations can be made without departing from the spirit of the present invention. Further, the present invention is not limited by each embodiment, and is limited only by the scope of the claims.

  The present invention can be widely used in fields such as residential environment facilities and vehicle windows.

Claims (7)

A durable transparent plate-like member,
The β-ferrandylene polymer having a specific gravity of 0.85 or more and less than 1.0 and a glass transition temperature of 100 ° C. or more is contained in an amount of 50 to 100% by mass with respect to the total mass of the durable transparent plate member. A durable transparent plate-like member characterized by that. 2. The durable transparent plate-like material according to claim 1, wherein the β-ferrandylene polymer is obtained by polymerizing at least one of β-ferrandolene represented by the following chemical formulas (I) and (II). Element.

The β ferrandylene polymer contains a total of 50 mass% or more of β ferrandylene units represented by the following chemical formulas (I-1), (I-2), (II-1) and (II-2). The durable transparent plate-like member according to claim 1 or 2, wherein

The durable transparent plate member according to any one of claims 1 to 3, wherein the β-ferrandylene polymer has a number average molecular weight Mn of 40,000 or more. The durable transparent plate-like member according to any one of claims 1 to 4, wherein at least a part of the olefinic carbon-carbon double bond of the β-ferrandylene polymer is hydrogenated. . The durable transparent plate-like member according to claim 5, wherein a hydrogenation rate of the β-ferrandylene polymer is 70% or more. The durable transparent plate member according to any one of claims 1 to 6, wherein the durable transparent plate member has a thickness of 0.5 mm to 500 mm.