WO2012161100A1 - Methacrylic resin composition and molded product thereof - Google Patents

Methacrylic resin composition and molded product thereof Download PDF

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Publication number
WO2012161100A1
WO2012161100A1 PCT/JP2012/062714 JP2012062714W WO2012161100A1 WO 2012161100 A1 WO2012161100 A1 WO 2012161100A1 JP 2012062714 W JP2012062714 W JP 2012062714W WO 2012161100 A1 WO2012161100 A1 WO 2012161100A1
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WIPO (PCT)
Prior art keywords
resin composition
methacrylic
methacrylic acid
mass
ester compound
Prior art date
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PCT/JP2012/062714
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French (fr)
Japanese (ja)
Inventor
智子 小倉
善光 生駒
斉藤　英一郎
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パナソニック株式会社
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Application filed by パナソニック株式会社 filed Critical パナソニック株式会社
Priority to JP2013516334A priority Critical patent/JPWO2012161100A1/en
Priority to CN201280023692.0A priority patent/CN103534284A/en
Publication of WO2012161100A1 publication Critical patent/WO2012161100A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate

Definitions

  • the present invention relates to a methacrylic resin composition and a molded body thereof, and in particular, can be suitably used as a substitute for a glass plate such as a window glass for vehicles or a building, a cover of a solar cell panel, and the like. is there.
  • Methacrylic acid ester compounds are used as various molding materials taking advantage of properties such as transparency, weather resistance, and surface hardness (see, for example, Patent Document 1).
  • the methacrylic ester compound has a large cure shrinkage and is difficult to mold. That is, the reaction of the vinyl group existing in the molecular chain occurs in the methacrylic acid ester compound.
  • the intermolecular distance (0.3 to 0.6 nm) between the vinyl groups existing before the reaction changes to a single bond (0.14 nm) by the reaction, so that the reaction causes contraction. .
  • the present invention has been made in view of the above points, and provides a methacrylic resin composition capable of reducing curing shrinkage while maintaining heat resistance and transparency, and a molded body using the same. It is intended.
  • the methacrylic resin composition according to the present invention includes a methacrylic acid ester compound containing at least one cyclic methacrylic acid ester, a polyfunctional unsaturated ester compound, and a radical polymerization start having a 10-hour half-life temperature of 50 to 100 ° C. It is characterized by containing an agent.
  • the ratio of the cyclic methacrylic acid ester is preferably 5 to 40% by mass of the methacrylic acid ester compound.
  • methacrylic resin composition of the present invention it is preferable to dissolve and contain an acrylic resin or a methacrylic resin.
  • the acrylic acid derivative or methacrylic acid derivative having a hindered topepyridine skeleton is preferably contained in an amount of 0.1 to 10% with respect to the total amount of the methacrylic ester compound.
  • the acrylic acid derivative or methacrylic acid derivative having a functional group that absorbs ultraviolet rays in the skeleton is contained in an amount of 0.1 to 10% with respect to the total amount of the methacrylic ester compound. It is preferable.
  • the molded body according to the present invention is formed by molding the methacrylic resin composition.
  • the molded product of the present invention preferably contains 5 to 40% by mass of the cyclic methacrylate.
  • the methacrylic resin composition and molded product thereof according to the present invention can reduce curing shrinkage while maintaining heat resistance and transparency.
  • the methacrylic resin composition according to the present invention is a radical polymerization initiator having a methacrylic acid ester compound containing at least one cyclic methacrylic acid ester, a polyfunctional unsaturated ester compound, and a 10-hour half-life temperature of 50 ° C. to 100 ° C. Containing the agent. Moreover, you may contain an acrylic resin as needed.
  • cyclic methacrylate examples include cyclohexyl methacrylate, phenoxy methacrylate, 4-t-butylcyclohexyl methacrylate, phenoxypolyethylene glycol methacrylate, dicyclopentenyloxyethyl methacrylate, tricyclodecyl methacrylate, phenoxyethyl methacrylate, benzyl methacrylate, adamantyl methacrylate.
  • Oxetane methacrylate, ⁇ -butyl lactone methacrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, tetrahydrofurfuryl methacrylate, and the like can be used. These may be used alone or in combination of two or more.
  • Such a cyclic methacrylic acid ester is particularly preferably contained in an amount of 5 to 40% by mass based on the total amount of the methacrylic acid ester compound. Curing shrinkage at the time of shaping
  • molding of a methacrylic-type resin composition can be reduced as content of cyclic methacrylate is this range.
  • methacrylic acid ester used in addition to the cyclic methacrylic acid ester as described above include, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, propyl methacrylate.
  • Isopropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, and the like can be used. These may be used alone or in combination of two or more.
  • polyfunctional unsaturated ester compound examples include divinylbenzene ethylene glycol dimethacrylate, divinylbenzene ethylene glycol diacrylate, ethylene glycol dimethacrylate, ethylene glycol acrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, Ethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol acrylate, 1,3-butylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 1,6- Hexanediol dimethacrylate, Bifunctional unsaturated esters such as opentyl glycol dimethacrylate, trimethylol ethane trimethacrylate, trimethylol ethane triacrylate, trimethylol propane trimethacrylate, trimethylol propane triacrylate, methyl
  • a tetrafunctional unsaturated ester such as a trifunctional unsaturated ester, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, dipropylene glycol dimethacrylate, or dipropylene glycol diacrylate can be used. These may be used alone or in combination of two or more.
  • diacyl peroxides As the radical polymerization initiator having a 10 hour half-life temperature of 50 to 100 ° C., diacyl peroxides, peroxyketals, alkyl peresters, and percarbonates can be used.
  • the 10-hour half-life temperature of the radical polymerization initiator is in the above range since insufficient curing and foaming can be suppressed.
  • the (meth) acrylic resin can be dissolved and blended as necessary.
  • “(Meth) acryl” refers to methacryl or acryl. By blending this (meth) acrylic resin, viscosity adjustment and improvement of moldability can be expected.
  • the (meth) acrylic resin used in the present invention include homopolymers or copolymers obtained from alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate and / or alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate.
  • a polymer can be used.
  • a copolymer of these monomers and other copolymerizable monomers can also be used.
  • polymethyl methacrylate polymethyl methacrylate (PMMA)
  • PMMA polymethyl methacrylate
  • the acrylic resin is preferably 10 to 30% by mass of the methacrylic ester compound.
  • the acrylic resin can be produced by a general polymerization technique such as solution polymerization, emulsion polymerization, suspension polymerization, and the production method is not particularly limited.
  • an acrylic acid derivative or a methacrylic acid derivative having a hindered topepyridine skeleton can be blended as necessary.
  • an improvement in light resistance can be expected. This is because the hindered topepyridine skeleton has an effect of capturing radicals generated by light (particularly ultraviolet rays) and inactivating them.
  • acrylic acid derivatives or methacrylic acid derivatives having a hindered topepyridine skeleton used in the present invention include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (for example, ADK STAB LA manufactured by ADEKA Corporation). -82), 2,2,6,6-tetramethyl-4-piperidyl methacrylate (for example, ADK STAB LA-87 manufactured by ADEKA Corporation) and the like.
  • the acrylic acid derivative or methacrylic acid derivative having such a hindered topepyridine skeleton preferably has a content of 0.1 to 10% by mass, particularly 1 to 3% by mass, based on the total amount of the methacrylic acid ester compound. It is preferable that it is a content rate.
  • the content of the acrylic acid derivative or methacrylic acid derivative having a hindered topepyridine skeleton is 0.1 to 10% by mass, the weather resistance can be improved without impairing the moldability of the methacrylic resin composition.
  • an acrylic acid derivative or a methacrylic acid derivative having a functional group that absorbs ultraviolet rays in the skeleton can be blended as necessary.
  • an improvement in weather resistance can be expected. This is because if a functional group that absorbs ultraviolet rays is added to the methacrylic acid ester polymer by polymerization, the ultraviolet rays can be absorbed on the surface or inside of the resin of the molded article while maintaining the properties of the acrylic resin. In other words, when it has ultraviolet absorbing ability, it is possible to suppress generation of radicals due to ultraviolet rays on the resin surface or inside of the molded body.
  • acrylic acid derivative or methacrylic acid derivative having a functional group that absorbs ultraviolet rays in the skeleton used in the present invention 1- (2-benzotriazole) -2-hydroxy-5- (2-methacryloyloxyethyl) benzene or this Similar compounds are mentioned.
  • Such an acrylic acid derivative or methacrylic acid derivative having a functional group that absorbs ultraviolet rays in the skeleton preferably has a content of 0.1 to 10% by mass, particularly 1 to 1%, based on the total amount of the methacrylic acid ester compound.
  • the content is preferably 3% by mass.
  • the methacrylic resin composition may contain an inorganic ultraviolet shielding agent such as titanium oxide, zinc oxide, cerium oxide or the like, as long as the transparency is not impaired, and other light stabilizers, antioxidants, heat A stabilizer, an antistatic agent, a heat ray reflective agent, a heat ray absorbent, a flame retardant, a lubricant, a pigment, a filler, and the like may be included.
  • an inorganic ultraviolet shielding agent such as titanium oxide, zinc oxide, cerium oxide or the like, as long as the transparency is not impaired, and other light stabilizers, antioxidants, heat A stabilizer, an antistatic agent, a heat ray reflective agent, a heat ray absorbent, a flame retardant, a lubricant, a pigment, a filler, and the like may be included.
  • the methacrylic resin composition of the present invention is prepared by blending a methacrylic acid ester compound, a polyfunctional unsaturated ester compound, and a radical polymerization initiator having a 10-hour half-life temperature of 50 ° C. to 100 ° C. be able to.
  • the blending ratio of each component is 0.5 to 20 parts by mass of the polyfunctional unsaturated ester compound and 50 hours to 100 ° C. of 10 hours half-life temperature with respect to 100 parts by mass of the methacrylic ester compound.
  • the radical polymerization initiator can be 0.1 to 5 parts by mass.
  • the molded body of the present invention can be obtained by injecting the above methacrylic resin composition into a mold such as a mold, a resin mold, or a glass mold and curing it in a specific temperature range under pressure or normal pressure. .
  • a methacrylic resin composition can be applied onto the above mold to obtain a film-like molded body.
  • a methacrylic resin composition containing a methacrylic acid ester compound containing at least one cyclic methacrylic acid ester, the polyfunctional unsaturated ester compound, and the radical polymerization initiator is described. It can be poured into a mold and cured by heating to obtain a molded product. At this time, the heat curing temperature is preferably in the range of 50 ° C.
  • the heat curing temperature is 50 ° C. or higher and lower than 100 ° C., a molded article having excellent heat resistance and transparency and less curing shrinkage can be obtained.
  • the methacrylic resin composition contains a cyclic methacrylic ester, it is excellent in heat resistance and transparency, and cure shrinkage is reduced.
  • a methacrylic resin molded article may be used for any application as long as the transparency and weather resistance are effectively used, and may be a film or sheet of about 30 ⁇ m to 1 mm. Good.
  • the methacrylic resin composition can be suitably used as described above for forming a thick article (thickness 1 to 10 mm).
  • a methacrylic resin composition as described above When a methacrylic resin composition as described above is molded, a polyfunctional unsaturated ester compound becomes a crosslinking point, and a molded product having a three-dimensional crosslinked structure can be obtained. Since this molded article has a three-dimensional crosslinked structure, it is superior in heat resistance to a molded article made of a methacrylic resin composition not having a three-dimensional crosslinked structure. Moreover, it is excellent in transparency, which is a feature of methacrylic acid ester.
  • Example 1 90 parts by mass of methyl methacrylate [Chemical Formula 1], 10 parts by mass of isobornyl methacrylate [Chemical Formula 2] as a cyclic methacrylate, and 1 part by mass of trimethylolpropane trimethacrylate [Chemical Formula 3] as a polyfunctional unsaturated ester compound Then, 0.3 part by mass of di- (3,5,5-trimethylhexanoyl) peroxide as a radical polymerization initiator was mixed to obtain a methacrylic resin composition. As the radical polymerization initiator, Trigonox 36-C75 manufactured by Kayaku Akzo Co., Ltd. was used. Next, the methacrylic resin composition thus prepared was poured into a mold and cured at 75 ° C. for 1 hour to obtain a molded body.
  • the radical polymerization initiator Trigonox 36-C75 manufactured by Kayaku Akzo Co., Ltd. was used.
  • Example 2 Molding was performed in the same manner as in Example 1 except that the blending ratio of methyl methacrylate and cyclic methacrylate was changed.
  • Example 5 Comparative Example 3 Molding was performed in the same manner as in Example 1 except that the type of radical polymerization initiator was changed.
  • Example 3 75 parts by mass of methyl methacrylate [Chemical Formula 1], 10 parts by mass of isobornyl methacrylate [Chemical Formula 2] as a cyclic methacrylate, 15 parts by mass of polymethyl methacrylate, and trimethylolpropanetri as a polyfunctional unsaturated ester compound 1 part by weight of methacrylate [Chemical Formula 3] and 0.3 part by weight of di- (3,5,5-trimethylhexanoyl) peroxide as a radical polymerization initiator were mixed to obtain a methacrylic resin composition.
  • the radical polymerization initiator Trigonox 36-C75 manufactured by Kayaku Akzo Co., Ltd. was used.
  • the methacrylic resin composition thus prepared was poured into a mold and cured at 75 ° C. for 1 hour to obtain a molded body.
  • Example 4 Molding was performed in the same manner as in Example 3 except that the blending ratio of methyl methacrylate and polymethyl methacrylate was changed.
  • Example 8 100 parts by mass of isobornyl methacrylate [Chemical Formula 2] as a cyclic methacrylate, 1 part by mass of trimethylolpropane trimethacrylate [Chemical Formula 3] as a polyfunctional unsaturated ester compound, and di- (3,5 as a radical polymerization initiator , 5-trimethylhexanoyl) peroxide 0.3 parts by mass was mixed to obtain a methacrylic resin composition.
  • the radical polymerization initiator Trigonox 36-C75 manufactured by Kayaku Akzo Co., Ltd. was used.
  • the methacrylic resin composition thus prepared was poured into a mold and cured at 75 ° C. for 1 hour to obtain a molded body.
  • Example 9 90 parts by mass of methyl methacrylate [Chemical Formula 1], 10 parts by mass of isobornyl methacrylate [Chemical Formula 2] as a cyclic methacrylic acid ester, and 1,2 methacrylic acid as an acrylic acid derivative or methacrylic acid derivative having a hindered topepyridine skeleton 1,6,6-pentamethyl-4-piperidyl [Chemical Formula 4] 1 part by mass, polyfunctional unsaturated ester compound trimethylolpropane trimethacrylate [Chemical Formula 3] 1 part by mass, radical polymerization initiator di- (3 , 5,5-trimethylhexanoyl) peroxide 0.3 parts by mass was mixed to obtain a methacrylic resin composition.
  • Trigonox 36-C75 of Kayaku Akzo Co., Ltd. was used as the radical polymerization initiator, and ADK STAB LA-82 manufactured by ADEKA Co., Ltd. was used as the acrylic acid derivative or methacrylic acid derivative having a hindered topepyridine skeleton. .
  • the methacrylic resin composition thus prepared was poured into a mold and cured at 75 ° C. for 1 hour to obtain a molded body.
  • Example 10 Molding was carried out in the same manner as in Example 9 except that the blending ratio of methyl methacrylate and a methacrylic acid derivative having a hindered topepyridine skeleton was changed.
  • Example 12 90 parts by mass of methyl methacrylate [Chemical Formula 1], 10 parts by mass of isobornyl methacrylate [Chemical Formula 2] as a cyclic methacrylic ester, and 1-acrylic acid derivative or methacrylic acid derivative having a functional group that absorbs ultraviolet rays in the skeleton.
  • the radical polymerization initiator is Trigonox 36-C75 of Kayaku Akzo Co., Ltd.
  • the acrylic acid derivative or methacrylic acid derivative having a functional group that absorbs ultraviolet rays as a skeleton is RUVA-93 manufactured by Otsuka Chemical Co., Ltd.
  • the methacrylic resin composition thus prepared was poured into a mold and cured at 75 ° C. for 1 hour to obtain a molded body.
  • Example 13 Molding was carried out in the same manner as in Example 12 except that the blending ratio of methyl methacrylate and a methallylic acid derivative having a functional group that absorbs ultraviolet rays in the skeleton was changed.
  • Example 15 90 parts by mass of methyl methacrylate [Chemical Formula 1], 10 parts by mass of isobornyl methacrylate [Chemical Formula 2] as a cyclic methacrylic acid ester, and 1,2 methacrylic acid as an acrylic acid derivative or methacrylic acid derivative having a hindered topepyridine skeleton 1 part of 2,6,6-pentamethyl-4-piperidyl [Chemical Formula 4] and 1- (2-benzotriazole) -2-hydroxy as an acrylic acid derivative or methacrylic acid derivative having a functional group that absorbs ultraviolet rays in the skeleton 1 part by mass of -5- (2-methacryloyloxyethyl) benzene [Chemical Formula 5], 1 part by mass of trimethylolpropane trimethacrylate [Chemical Formula 3] as a polyfunctional unsaturated ester compound, and di- (3 , 5,5-trimethylhexanoyl) peroxide 0.3 parts by mass,
  • the radical polymerization initiator is Trigonox 36-C75 manufactured by Kayaku Akzo Co., Ltd.
  • the acrylic acid derivative or methacrylic acid derivative having a hindered topepyridine skeleton is ADK STAB LA-82 manufactured by ADEKA Co., Ltd. RUVA-93 manufactured by Otsuka Chemical Co., Ltd. was used as an acrylic acid derivative or a methacrylic acid derivative having a functional group that absorbs.
  • the methacrylic resin composition thus prepared was poured into a mold and cured at 75 ° C. for 1 hour to obtain a molded body.
  • the weather resistance test was conducted using DPWL-5R manufactured by Suga Test Instruments. The test conditions were based on JIS A 1415 and JIS K 7350-3. After six samples were installed in a dew panel weather meter, the black panel temperature was set to 63 ° C (during irradiation), the irradiance was set to 30 W / m 2 (300 to 400 nm), irradiation for 4 hours, and extinction (condensation) for 4 hours. The test cycle was 200 hours. As an evaluation method, a white plate was placed on the back surface of the resin and measured with a color difference meter, and the change in color before and after the test was shown as a ⁇ E value.
  • Examples 1 to 8 have the same transparency, excellent heat resistance, and suppressed curing shrinkage, as compared with Comparative Examples 1 and 2.
  • the weather resistance is further excellent. From this, when a cyclic methacrylic ester is blended with a methacrylic resin composition, curing shrinkage can be reduced while maintaining heat resistance and transparency. Furthermore, when one or both of the hindered piperidine skeleton and the functional group that absorbs ultraviolet rays are included in the skeleton, the weather resistance of the molded article can be improved. it can.

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Abstract

The purpose of the present invention is to provide a methacrylic resin composition whereby the occurrence of shrinkage upon curing can be reduced while keeping heat resistance and transparency. This methacrylic resin composition comprises a methacrylic acid ester compound comprising at least one cyclic methacrylic acid ester, a polyfunctional unsaturated ester compound, and a radical polymerization initiator having a 10-hour half-life temperature of 50-100ºC.

Description

メタクリル系樹脂組成物及びその成形体Methacrylic resin composition and molded body thereof
　本発明は、メタクリル系樹脂組成物及びその成形体に関するものであり、特に、車両用や建築用の窓ガラス、太陽電池パネルのカバーなどのガラス板の代用品として好適に用いることができるものである。 The present invention relates to a methacrylic resin composition and a molded body thereof, and in particular, can be suitably used as a substitute for a glass plate such as a window glass for vehicles or a building, a cover of a solar cell panel, and the like. is there.
　メタクリル酸エステル化合物は透明性、耐候性、表面硬度などの特性を生かして各種の成形材料として用いられている（例えば、特許文献１参照）。しかしながら、メタクリル酸エステル化合物は硬化収縮が大きく、成形が困難である。すなわち、メタクリル酸エステル化合物は分子鎖中に存在するビニル基の反応が生じる。このとき、反応前に存在するビニル基間の分子間距離（０．３～０．６ｎｍ）が反応により単結合（０．１４ｎｍ）に変化するため、反応により収縮が生じることが知られている。 Methacrylic acid ester compounds are used as various molding materials taking advantage of properties such as transparency, weather resistance, and surface hardness (see, for example, Patent Document 1). However, the methacrylic ester compound has a large cure shrinkage and is difficult to mold. That is, the reaction of the vinyl group existing in the molecular chain occurs in the methacrylic acid ester compound. At this time, it is known that the intermolecular distance (0.3 to 0.6 nm) between the vinyl groups existing before the reaction changes to a single bond (0.14 nm) by the reaction, so that the reaction causes contraction. .
　近年、このような硬化収縮の低減に対して、さまざまな検討がなされている。一般に、長鎖アルキル（メタ）アクリレートのようにアクリル当量の小さい材料やガラス転移温度の低い材料の添加により硬化収縮を低減できることが知られている。しかしながら、これらの手法では硬化収縮を低減できるものの耐熱性が低下する。そこで、耐熱性を維持しながら硬化収縮を低減する手法として、メタクリル酸エステルよりも硬化収縮が小さい無機粒子の添加が行われている。この場合、無機粒子を添加することにより大幅に硬化収縮を低減できるものの、透明性が大幅に低下する。 In recent years, various studies have been made on the reduction of such curing shrinkage. In general, it is known that curing shrinkage can be reduced by the addition of a material having a low acrylic equivalent, such as a long-chain alkyl (meth) acrylate, or a material having a low glass transition temperature. However, although these methods can reduce curing shrinkage, the heat resistance is reduced. Therefore, as a method of reducing the curing shrinkage while maintaining heat resistance, inorganic particles having a smaller curing shrinkage than methacrylic acid esters are added. In this case, the addition of inorganic particles can significantly reduce curing shrinkage, but the transparency is greatly reduced.
国際公開ＷＯ９８／５５８８５号International Publication WO98 / 55885
　本発明は上記の点に鑑みてなされたものであり、耐熱性及び透明性を維持したまま硬化収縮を低減することができるメタクリル系樹脂組成物、及びこれを用いた成形体を提供することを目的としたものである。 The present invention has been made in view of the above points, and provides a methacrylic resin composition capable of reducing curing shrinkage while maintaining heat resistance and transparency, and a molded body using the same. It is intended.
　本発明に係るメタクリル系樹脂組成物は、少なくとも一種類の環状メタクリル酸エステルを含むメタクリル酸エステル化合物と、多官能不飽和エステル化合物と、１０時間半減期温度が５０～１００℃であるラジカル重合開始剤とを含有して成ることを特徴とするものである。 The methacrylic resin composition according to the present invention includes a methacrylic acid ester compound containing at least one cyclic methacrylic acid ester, a polyfunctional unsaturated ester compound, and a radical polymerization start having a 10-hour half-life temperature of 50 to 100 ° C. It is characterized by containing an agent.
　本発明のメタクリル系樹脂組成物にあっては、前記環状メタクリル酸エステルの比率が前記メタクリル酸エステル化合物の５～４０質量％であることが好ましい。 In the methacrylic resin composition of the present invention, the ratio of the cyclic methacrylic acid ester is preferably 5 to 40% by mass of the methacrylic acid ester compound.
　本発明のメタクリル系樹脂組成物にあっては、アクリル樹脂又はメタクリル樹脂を溶解させて含有させることが好ましい。 In the methacrylic resin composition of the present invention, it is preferable to dissolve and contain an acrylic resin or a methacrylic resin.
　本発明のメタクリル系樹脂組成物にあっては、ヒンダートペピリジン骨格を有するアクリル酸誘導体又はメタクリル酸誘導体を前記メタクリル酸エステル化合物の全量に対して０．１以上１０％以下含有することが好ましい。 In the methacrylic resin composition of the present invention, the acrylic acid derivative or methacrylic acid derivative having a hindered topepyridine skeleton is preferably contained in an amount of 0.1 to 10% with respect to the total amount of the methacrylic ester compound.
　本発明のメタクリル系樹脂組成物にあっては、紫外線を吸収する官能基を骨格に有するアクリル酸誘導体又はメタクリル酸誘導体を前記メタクリル酸エステル化合物の全量に対して０．１以上１０％以下含有することが好ましい。 In the methacrylic resin composition of the present invention, the acrylic acid derivative or methacrylic acid derivative having a functional group that absorbs ultraviolet rays in the skeleton is contained in an amount of 0.1 to 10% with respect to the total amount of the methacrylic ester compound. It is preferable.
　本発明に係る成形体は、前記メタクリル系樹脂組成物を成形して成ることを特徴とするものである。 The molded body according to the present invention is formed by molding the methacrylic resin composition.
　本発明の成形体にあっては、前記環状メタクリル酸エステルを５～４０質量％含有していることが好ましい。 The molded product of the present invention preferably contains 5 to 40% by mass of the cyclic methacrylate.
　本発明のメタクリル系樹脂組成物及びその成形体は、耐熱性及び透明性を維持したまま硬化収縮を低減することができるものである。 The methacrylic resin composition and molded product thereof according to the present invention can reduce curing shrinkage while maintaining heat resistance and transparency.
　以下、本発明を実施するための形態を説明する。 Hereinafter, modes for carrying out the present invention will be described.
　本発明におけるメタクリル系樹脂組成物は、環状メタクリル酸エステルを少なくとも１種含有するメタクリル酸エステル化合物と、多官能不飽和エステル化合物と、１０時間半減期温度が５０℃～１００℃であるラジカル重合開始剤とを含有する。また、必要に応じアクリル樹脂を含有してもよい。 The methacrylic resin composition according to the present invention is a radical polymerization initiator having a methacrylic acid ester compound containing at least one cyclic methacrylic acid ester, a polyfunctional unsaturated ester compound, and a 10-hour half-life temperature of 50 ° C. to 100 ° C. Containing the agent. Moreover, you may contain an acrylic resin as needed.
　上記の環状メタクリル酸エステルとしては、例えばシクロヘキシルメタクリレート、フェノキシメタクリレート、４‐ｔ‐ブチルシクロヘキシルメタクリレート、フェノキシポリエチレングリコールメタクリレート、ジシクロペンテニルオキシエチルメタクリレート、トリシクロデシルメタクリレート、フェノキシエチルメタクリレート、ベンジルメタクリレート、アダマンチルメタクリレート、オキセタンメタクリレート、γ‐ブチルラクトンメタクリレート、イソボルニルメタクリレート、ジシクロペンテニルメタクリレート、テトラヒドロフルフリルメタクリレートなどを用いることができる。これらは１種で使用してもよいし、２種以上が併用されてもよい。 Examples of the cyclic methacrylate include cyclohexyl methacrylate, phenoxy methacrylate, 4-t-butylcyclohexyl methacrylate, phenoxypolyethylene glycol methacrylate, dicyclopentenyloxyethyl methacrylate, tricyclodecyl methacrylate, phenoxyethyl methacrylate, benzyl methacrylate, adamantyl methacrylate. Oxetane methacrylate, γ-butyl lactone methacrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, tetrahydrofurfuryl methacrylate, and the like can be used. These may be used alone or in combination of two or more.
　このような環状メタクリル酸エステルは、特に、メタクリル酸エステル化合物の全量に対して５～４０質量％の含有量であることが好ましい。環状メタクリル酸エステルの含有量がこの範囲であると、メタクリル系樹脂組成物の成形時の硬化収縮を低減することができる。 Such a cyclic methacrylic acid ester is particularly preferably contained in an amount of 5 to 40% by mass based on the total amount of the methacrylic acid ester compound. Curing shrinkage at the time of shaping | molding of a methacrylic-type resin composition can be reduced as content of cyclic methacrylate is this range.
　上記のような環状メタクリル酸エステルの他に用いられるメタクリル酸エステルとしては、例えば、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸イソブチル、メタクリル酸２‐エチルヘキシル、メタクリル酸ラウリル、メタクリル酸プロピル、メタクリル酸イソプロピル、メタクリル酸２‐ヒドロキシエチル、メタクリル酸２‐ヒドロキシプロピル、メタクリル酸３‐ヒドロキシプロピルなどを、用いることができる。これらは１種で使用してもよいし、２種以上が併用されてもよい。 Examples of the methacrylic acid ester used in addition to the cyclic methacrylic acid ester as described above include, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, propyl methacrylate. , Isopropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, and the like can be used. These may be used alone or in combination of two or more.
　上記の多官能不飽和エステル化合物としては、例えばジビニルベンゼンエチレングリコールジメタクリレート、ジビニルベンゼンエチレングリコールジアクリレート、エチレングリコールジメタクリレート、エチレングリコールアクリレート、ジエチレングリコールジメタクリレート、ジエチレングリコールジアクリレート、トリエチレングリコールジメタクリレート、トリエチレングリコールジアクリレート、ポリエチレングリコールジメタクリレート、ポリエチレングリコールアクリレート、１，３‐ブチレングリコールジメタクリレート、１，３‐プロピレングリコールジメタクリレート、１，４‐ブチレングリコールジメタクリレート、ポリプロピレングリコールジメタクリレート、１，６‐ヘキサンジオールジメタクリレート、ネオペンチルグリコールジメタクリレートなどの２官能不飽和エステル、トリメチロールエタントリメタクリレート、トリメチロールエタントリアクリレート、トリメチロールプロパントリメタクリレート、トリメチロールプロパントリアクリレート、テトラメチロールメタントリメタクリレート、テトラメチロールメタントリアクリレートなどの３官能不飽和エステル、テトラメチロールメタンテトラメタクリレート、テトラメチロールメタンテトラアクリレート、ジプロピレングリコールジメタクリレート、ジプロピレングリコールジアクリレートなどの４官能不飽和エステルを用いることができる。これらは１種で使用してもよいし、２種以上が併用されてもよい。 Examples of the polyfunctional unsaturated ester compound include divinylbenzene ethylene glycol dimethacrylate, divinylbenzene ethylene glycol diacrylate, ethylene glycol dimethacrylate, ethylene glycol acrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, Ethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol acrylate, 1,3-butylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 1,6- Hexanediol dimethacrylate, Bifunctional unsaturated esters such as opentyl glycol dimethacrylate, trimethylol ethane trimethacrylate, trimethylol ethane triacrylate, trimethylol propane trimethacrylate, trimethylol propane triacrylate, tetramethylol methane trimethacrylate, tetramethylol methane triacrylate, etc. A tetrafunctional unsaturated ester such as a trifunctional unsaturated ester, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, dipropylene glycol dimethacrylate, or dipropylene glycol diacrylate can be used. These may be used alone or in combination of two or more.
　上記の１０時間半減期温度が５０～１００℃であるラジカル重合開始剤としては、ジアシルパーオキサイド類、パーオキシケタール類、アルキルパーエステル類、パーカーボネート類を用いることができる。例えばジ‐（３，３，５‐トリメチルヘキサノイル）パーオキサイド、ジ‐ラウロイルパーオキサイド、ジベンゾイルパーオキサイド、１，１‐ジ‐（ｔ‐ブチルパーオキシ）シクロヘキサン、２，２‐ジ‐（ｔ‐アミルパーオキシ）ブタン、２，２‐ジ‐（４，４‐ジ‐ｔ‐（ブチルパーオキシ）シクロヘキシル）プロパン、ｔ‐ブチルパーオキシネオヘプタネート、ピバリン酸ｔ‐ヘキシルパーオキサイド、ピバリン酸ｔ‐ブチルパーオキサイド、１，１，３，３‐テトラメチルブチルパーオキシ‐２‐エチルヘキサネート、ジコハク酸パーオキサイド、２，５‐ジメチル‐２，５‐ジ（２‐エチルヘキサノイルパーオキシ）ヘキサン、ｔ‐ヘキシルパーオキシ‐２‐エチルヘキサネート、ジ（４‐メチルベンゾイル）パーオキサイド、ｔ‐アミルパーオキシル‐２‐エチルヘキサネート、ジ‐ｔ‐ブチルパーオキシヘキサハイドロテレフタレート、ｔ‐アミルパーオキシ３，３，５‐トリメチルヘキサネート、ｔ‐アミルパーオキシイソプロピルカーボネート、ｔ‐ブチルパーオキシイソプロピルカーボネート、ｔ‐ブチルパーオキシ‐２‐エチルヘキシルカーボネート、１，６‐ジ‐（ｔ‐ブチルパーオキシカルボニロキシ）ヘキサン、ｔ‐ブチルパーオキシジエチルアセテート、１，１‐ジ（ｔ‐ブチルパーオキシ）‐２‐メチルシクロヘキサン、１，１‐ジ（ｔ‐ヘキシルパーオキシ）‐３，３，５‐トリメチルシクロヘキサン、１，１‐ジ（ｔ‐ヘキシルパーオキシ）シクロヘキサン、ｔ‐ヘキシルパーオキシイソプロピルカーボネート、マレンイン酸ｔ‐ブチルパーオキサイド、ｔ‐ブチルパーオキシ‐３，３，５‐トリメチルヘキサネート、ｔ‐ブチルパーオキシラウレート、ｔ‐ヘキシルパーオキシベンゾネート、２，５‐ジメチル‐２，５‐ジ（ベンゾイルパーオキシ）ヘキサンなどの公知の有機過酸化物が挙げられ、これらは１種で使用してもよいし、２種以上が併用されてもよい。尚、１０時間半減期温度とは、公知の指標であって、熱により重合開始剤が分解し、１０時間経過後の重合開始剤の濃度が初期の半分に減るのに必要な温度を意味している。 As the radical polymerization initiator having a 10 hour half-life temperature of 50 to 100 ° C., diacyl peroxides, peroxyketals, alkyl peresters, and percarbonates can be used. For example, di- (3,3,5-trimethylhexanoyl) peroxide, di-lauroyl peroxide, dibenzoyl peroxide, 1,1-di- (t-butylperoxy) cyclohexane, 2,2-di- ( t-amylperoxy) butane, 2,2-di- (4,4-di-t- (butylperoxy) cyclohexyl) propane, t-butylperoxyneoheptanate, t-hexyl peroxide pivalate, pivalin T-butyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxide) Oxy) hexane, t-hexylperoxy-2-ethylhexanate, di (4-methylbenzoyl) peroxide, -Amylperoxyl-2-ethylhexanate, di-t-butylperoxyhexahydroterephthalate, t-amylperoxy3,3,5-trimethylhexanate, t-amylperoxyisopropyl carbonate, t-butylperoxy Isopropyl carbonate, t-butylperoxy-2-ethylhexyl carbonate, 1,6-di- (t-butylperoxycarbonyloxy) hexane, t-butylperoxydiethyl acetate, 1,1-di (t-butylperoxide) Oxy) -2-methylcyclohexane, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, t-hexylperoxyisopropyl Carbonate, t-butyl paramalenate Oxide, t-butylperoxy-3,3,5-trimethylhexanate, t-butylperoxylaurate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) Well-known organic peroxides, such as hexane, are mentioned, These may be used by 1 type and 2 or more types may be used together. The 10-hour half-life temperature is a well-known index, and means a temperature necessary for the polymerization initiator to decompose by heat and the concentration of the polymerization initiator to decrease to half of the initial value after 10 hours. ing.
　ラジカル重合開始剤の１０時間半減期温度が上記の範囲であると、硬化不足や発泡などを抑えることができて好ましい。 It is preferable that the 10-hour half-life temperature of the radical polymerization initiator is in the above range since insufficient curing and foaming can be suppressed.
　本発明では、必要に応じて（メタ）アクリル樹脂を溶解させて配合することができる。尚、「（メタ）アクリル」とはメタクリル又はアクリルのことを指す。この（メタ）アクリル樹脂を配合することで、粘度調製や成形性の向上が期待できる。本発明で用いられる（メタ）アクリル樹脂としては、例えば、メチルアクリレート、エチルアクリレート、ブチルアクリレートなどのアルキルアクリレート及び／又はメチルメタクリレート、エチルメタクリレート、ブチルメタクリレートなどのアルキルメタクリレートから得られる単独重合体又は共重合体を用いることができる。また、これらのモノマーと、他の共重合可能なモノマーとの共重合体も用いることができる。特に、反応性や耐候性、透明性の点からポリメチルメタクリレート（ポリメタクリル酸メチル（ＰＭＭＡ））が好ましい。また、特に、アクリル樹脂はメタクリル酸エステル化合物の１０～３０質量％であることが好ましい。このアクリル系樹脂は溶液重合、乳化重合、懸濁重合などの一般の重合手法によって製造が可能であり、またその製造方法には特に制限はない。 In the present invention, the (meth) acrylic resin can be dissolved and blended as necessary. “(Meth) acryl” refers to methacryl or acryl. By blending this (meth) acrylic resin, viscosity adjustment and improvement of moldability can be expected. Examples of the (meth) acrylic resin used in the present invention include homopolymers or copolymers obtained from alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate and / or alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate. A polymer can be used. A copolymer of these monomers and other copolymerizable monomers can also be used. In particular, polymethyl methacrylate (polymethyl methacrylate (PMMA)) is preferable from the viewpoint of reactivity, weather resistance, and transparency. In particular, the acrylic resin is preferably 10 to 30% by mass of the methacrylic ester compound. The acrylic resin can be produced by a general polymerization technique such as solution polymerization, emulsion polymerization, suspension polymerization, and the production method is not particularly limited.
　従来のメタクリル系樹脂組成物から成る成形体に光を照射すると、経時的に透明性が低下する場合がある。これは、メタクリル系樹脂組成物のモノマーに不純物として含まれるヒドロキノンが、紫外線により生じたラジカルにより、ベンゾキノンに変換されることが原因であると考えられる。 When light is applied to a molded body made of a conventional methacrylic resin composition, the transparency may deteriorate over time. This is considered to be because hydroquinone contained as an impurity in the monomer of the methacrylic resin composition is converted to benzoquinone by radicals generated by ultraviolet rays.
　そこで、本発明では、必要に応じてヒンダートペピリジン骨格を有するアクリル酸誘導体又はメタクリル酸誘導体を配合することができる。このヒンダートペピリジン骨格を有するアクリル酸誘導体又はメタクリル酸誘導体を配合することで、耐光性の向上が期待できる。なぜなら、ヒンダートペピリジン骨格は、光（特に紫外線）により発生したラジカルを捕捉し、これを不活性化する効果があるからである。本発明で用いられるヒンダートペピリジン骨格を有するアクリル酸誘導体又はメタクリル酸誘導体としては、メタクリル酸１,２,２,６,６－ペンタメチル－４－ピペリジル（例えば、（株）ＡＤＥＫＡ製のＡＤＫ　ＳＴＡＢ　ＬＡ－８２）、メタクリル酸２,２,６,６－テトラメチル－４－ピペリジル（例えば、（株）ＡＤＥＫＡ製のＡＤＫ　ＳＴＡＢ　ＬＡ－８７）などが挙げられる。 Therefore, in the present invention, an acrylic acid derivative or a methacrylic acid derivative having a hindered topepyridine skeleton can be blended as necessary. By adding an acrylic acid derivative or a methacrylic acid derivative having this hindered topepyridine skeleton, an improvement in light resistance can be expected. This is because the hindered topepyridine skeleton has an effect of capturing radicals generated by light (particularly ultraviolet rays) and inactivating them. Examples of acrylic acid derivatives or methacrylic acid derivatives having a hindered topepyridine skeleton used in the present invention include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (for example, ADK STAB LA manufactured by ADEKA Corporation). -82), 2,2,6,6-tetramethyl-4-piperidyl methacrylate (for example, ADK STAB LA-87 manufactured by ADEKA Corporation) and the like.
　このようなヒンダートペピリジン骨格を有するアクリル酸誘導体又はメタクリル酸誘導体は、メタクリル酸エステル化合物の全量に対して０．１～１０質量％の含有量であることが好ましく、特に1～３質量％の含有率であることが好ましい。ヒンダートペピリジン骨格を有するアクリル酸誘導体又はメタクリル酸誘導体の含有量が０．１～１０質量％であると、メタクリル系樹脂組成物の成形性を損ねることなく、耐候性を向上させることができる。 The acrylic acid derivative or methacrylic acid derivative having such a hindered topepyridine skeleton preferably has a content of 0.1 to 10% by mass, particularly 1 to 3% by mass, based on the total amount of the methacrylic acid ester compound. It is preferable that it is a content rate. When the content of the acrylic acid derivative or methacrylic acid derivative having a hindered topepyridine skeleton is 0.1 to 10% by mass, the weather resistance can be improved without impairing the moldability of the methacrylic resin composition.
　また、本発明では、必要に応じて紫外線を吸収する官能基を骨格に有するアクリル酸誘導体又はメタクリル酸誘導体を配合することができる。この紫外線を吸収する官能基を骨格に有するアクリル酸誘導体又はメタクリル酸誘導体を配合することで、耐候性の向上が期待できる。なぜなら、重合により、メタクリル酸エステルのポリマーに紫外線を吸収する官能基を持たせると、アクリル系樹脂の特性を維持しながら、成形体の樹脂の表面若しくは内部で、紫外線を吸収することができる。つまり紫外線吸収能を有していると、成形体の樹脂表面若しくは内部で紫外線によるラジカルの発生を抑制することができるからである。本発明で用いられる紫外線を吸収する官能基を骨格に有するアクリル酸誘導体又はメタクリル酸誘導体としては、１－（２－ベンゾトリアゾール）－２－ヒドロキシ－５－（２－メタクリロイルオキシエチル）ベンゼン又はこの類似化合物が挙げられる。 In the present invention, an acrylic acid derivative or a methacrylic acid derivative having a functional group that absorbs ultraviolet rays in the skeleton can be blended as necessary. By adding an acrylic acid derivative or a methacrylic acid derivative having a functional group that absorbs ultraviolet rays in the skeleton, an improvement in weather resistance can be expected. This is because if a functional group that absorbs ultraviolet rays is added to the methacrylic acid ester polymer by polymerization, the ultraviolet rays can be absorbed on the surface or inside of the resin of the molded article while maintaining the properties of the acrylic resin. In other words, when it has ultraviolet absorbing ability, it is possible to suppress generation of radicals due to ultraviolet rays on the resin surface or inside of the molded body. As the acrylic acid derivative or methacrylic acid derivative having a functional group that absorbs ultraviolet rays in the skeleton used in the present invention, 1- (2-benzotriazole) -2-hydroxy-5- (2-methacryloyloxyethyl) benzene or this Similar compounds are mentioned.
　このような紫外線を吸収する官能基を骨格に有するアクリル酸誘導体又はメタクリル酸誘導体は、メタクリル酸エステル化合物の全量に対して０．１～１０質量％の含有量であることが好ましく、特に1～３質量％の含有率であることが好ましい。紫外線を吸収する官能基を骨格に有するアクリル酸誘導体又はメタクリル酸誘導体の含有量が０．１～１０質量％であると、メタクリル系樹脂組成物の透明性を損ねることなくのを耐候性を向上させることができる。 Such an acrylic acid derivative or methacrylic acid derivative having a functional group that absorbs ultraviolet rays in the skeleton preferably has a content of 0.1 to 10% by mass, particularly 1 to 1%, based on the total amount of the methacrylic acid ester compound. The content is preferably 3% by mass. When the content of the acrylic acid derivative or methacrylic acid derivative having a functional group that absorbs ultraviolet rays in the skeleton is 0.1 to 10% by mass, the weather resistance is improved without impairing the transparency of the methacrylic resin composition. Can be made.
　上記メタクリル系樹脂組成物は、透明性を損なわない程度に、酸化チタン、酸化亜鉛、酸化セリウム等無機系紫外線遮蔽剤を含有してもよく、また、他の光安定剤、酸化防止剤、熱安定剤、帯電防止剤、熱線反射剤、熱線吸収剤、難燃剤、滑剤、顔料、フィラー等を含んでいてもよい。 The methacrylic resin composition may contain an inorganic ultraviolet shielding agent such as titanium oxide, zinc oxide, cerium oxide or the like, as long as the transparency is not impaired, and other light stabilizers, antioxidants, heat A stabilizer, an antistatic agent, a heat ray reflective agent, a heat ray absorbent, a flame retardant, a lubricant, a pigment, a filler, and the like may be included.
　そして、本発明のメタクリル系樹脂組成物は、メタクリル酸エステル化合物と、多官能不飽和エステル化合物と、１０時間半減期温度が５０℃～１００℃であるラジカル重合開始剤と配合することにより調製することができる。ここで、各成分の配合割合は、メタクリル酸エステル化合物の１００質量部に対して、多官能不飽和エステル化合物が０．５～２０質量部、１０時間半減期温度が５０℃～１００℃であるラジカル重合開始剤が０．１～５質量部とすることができる。この配合割合で各成分を配合すると、耐熱性や透明性に優れ、硬化収縮が低減されるメタクリル系樹脂組成物を得ることができる。 The methacrylic resin composition of the present invention is prepared by blending a methacrylic acid ester compound, a polyfunctional unsaturated ester compound, and a radical polymerization initiator having a 10-hour half-life temperature of 50 ° C. to 100 ° C. be able to. Here, the blending ratio of each component is 0.5 to 20 parts by mass of the polyfunctional unsaturated ester compound and 50 hours to 100 ° C. of 10 hours half-life temperature with respect to 100 parts by mass of the methacrylic ester compound. The radical polymerization initiator can be 0.1 to 5 parts by mass. When each component is blended at this blending ratio, a methacrylic resin composition having excellent heat resistance and transparency and reduced cure shrinkage can be obtained.
　本発明の成形体は、上記のメタクリル系樹脂組成物を金型、樹脂型、ガラス型などの型枠に注入し、加圧または常圧下、ある特定の温度範囲で硬化させて得ることができる。また、メタクリル系樹脂組成物を上記型枠上に塗布し、フィルム状の成形体を得ることもできる。その一例を説明すると、上記の少なくとも１種類の環状メタクリル酸エステルを含むメタクリル酸エステル化合物と、上記の多官能不飽和エステル化合物と、上記のラジカル重合開始剤とを含有するメタクリル系樹脂組成物を型に注入して、加熱硬化させて、成形体を得ることができる。このとき、加熱硬化温度は５０℃以上１００℃未満、特に６０℃以上９０℃未満の範囲にあることが好ましい。加熱硬化温度が５０℃以上１００℃未満であると、耐熱性や透明性に優れ、硬化収縮の少ない成形体を得ることができる。 The molded body of the present invention can be obtained by injecting the above methacrylic resin composition into a mold such as a mold, a resin mold, or a glass mold and curing it in a specific temperature range under pressure or normal pressure. . Alternatively, a methacrylic resin composition can be applied onto the above mold to obtain a film-like molded body. For example, a methacrylic resin composition containing a methacrylic acid ester compound containing at least one cyclic methacrylic acid ester, the polyfunctional unsaturated ester compound, and the radical polymerization initiator is described. It can be poured into a mold and cured by heating to obtain a molded product. At this time, the heat curing temperature is preferably in the range of 50 ° C. or higher and lower than 100 ° C., particularly 60 ° C. or higher and lower than 90 ° C. When the heat curing temperature is 50 ° C. or higher and lower than 100 ° C., a molded article having excellent heat resistance and transparency and less curing shrinkage can be obtained.
　そして、上記のようにメタクリル系樹脂組成物が環状メタクリル酸エステルを含有することで、耐熱性及び透明性に優れるとともに、硬化収縮が低減されるものである。このようなメタクリル系樹脂成形体は、透明性、耐候性が有効に利用される用途であればいずれの用途に使用してもよく、また、３０μｍ～１ｍｍ程度のフィルムまたはシート状であってもよい。特に、硬化収縮が少ないため、厚物（厚み１～１０ｍｍ）の成形体を成形するのに、上記のようにメタクリル系樹脂組成物を好適に用いることができる。 And as mentioned above, when the methacrylic resin composition contains a cyclic methacrylic ester, it is excellent in heat resistance and transparency, and cure shrinkage is reduced. Such a methacrylic resin molded article may be used for any application as long as the transparency and weather resistance are effectively used, and may be a film or sheet of about 30 μm to 1 mm. Good. In particular, since there is little cure shrinkage, the methacrylic resin composition can be suitably used as described above for forming a thick article (thickness 1 to 10 mm).
　上記のようなメタクリル系樹脂組成物を成形すると、多官能不飽和エステル化合物が架橋点となり、３次元架橋構造を有する成形体を得ることができる。この成形体は３次元架橋構造を有するため、３次元架橋構造を有さないメタクリル系樹脂組成物から成る成形体よりも耐熱性に優れている。また、メタクリル酸エステルの特徴である、透明性にも優れている。また、硬化収縮を抑える環状メタクリル酸エステルを用いることで、多官能不飽和エステル化合物による３次元架橋構造を形成しながら、耐熱性、透明性に優れ、硬化収縮の少ない成形体を得ることができる。 When a methacrylic resin composition as described above is molded, a polyfunctional unsaturated ester compound becomes a crosslinking point, and a molded product having a three-dimensional crosslinked structure can be obtained. Since this molded article has a three-dimensional crosslinked structure, it is superior in heat resistance to a molded article made of a methacrylic resin composition not having a three-dimensional crosslinked structure. Moreover, it is excellent in transparency, which is a feature of methacrylic acid ester. In addition, by using a cyclic methacrylic acid ester that suppresses curing shrinkage, it is possible to obtain a molded article that is excellent in heat resistance and transparency and has little curing shrinkage while forming a three-dimensional crosslinked structure with a polyfunctional unsaturated ester compound. .
　以下に、本発明を実施例によって具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to only these examples.
　（実施例１）
　メタクリル酸メチル［化１］９０質量部に、環状メタクリル酸エステルとしてイソボルニルメタクリレート［化２］１０質量部と、多官能不飽和エステル化合物としてトリメチロールプロパントリメタクリレート［化３］１質量部と、ラジカル重合開始剤としてジ‐（３，５，５－トリメチルヘキサノイル）パーオキサイド０．３質量部を混合し、メタクリル系樹脂組成物を得た。なお、ラジカル重合開始剤は化薬アクゾ（株）のトリゴノックス３６－Ｃ７５を用いた。つぎに、このように調製したメタクリル系樹脂組成物を金型に流し込み、７５℃で１時間の条件で硬化させ、成形体を得た。 Example 1
90 parts by mass of methyl methacrylate [Chemical Formula 1], 10 parts by mass of isobornyl methacrylate [Chemical Formula 2] as a cyclic methacrylate, and 1 part by mass of trimethylolpropane trimethacrylate [Chemical Formula 3] as a polyfunctional unsaturated ester compound Then, 0.3 part by mass of di- (3,5,5-trimethylhexanoyl) peroxide as a radical polymerization initiator was mixed to obtain a methacrylic resin composition. As the radical polymerization initiator, Trigonox 36-C75 manufactured by Kayaku Akzo Co., Ltd. was used. Next, the methacrylic resin composition thus prepared was poured into a mold and cured at 75 ° C. for 1 hour to obtain a molded body.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
 　（実施例２、６、７）
　メタクリル酸メチルと環状メタクリル酸エステルの配合比率を変えた点を除いては実施例１と同様にして成形した。
Figure JPOXMLDOC01-appb-C000003
 (Examples 2, 6, and 7)
Molding was performed in the same manner as in Example 1 except that the blending ratio of methyl methacrylate and cyclic methacrylate was changed.
　（実施例５、比較例３）
ラジカル重合開始剤の種類を変えた点を除いては実施例１と同様にして成形した。 (Example 5, Comparative Example 3)
Molding was performed in the same manner as in Example 1 except that the type of radical polymerization initiator was changed.
　（実施例３）
　メタクリル酸メチル［化１］７５質量部に、環状メタクリル酸エステルとしてイソボルニルメタクリレート［化２］１０質量部と、ポリメタクリル酸メチル１５質量部と、多官能不飽和エステル化合物としてトリメチロールプロパントリメタクリレート［化３］１質量部と、ラジカル重合開始剤としてジ‐（３，５，５－トリメチルヘキサノイル）パーオキサイド０．３質量部を混合し、メタクリル系樹脂組成物を得た。なお、ラジカル重合開始剤は化薬アクゾ（株）のトリゴノックス３６－Ｃ７５を用いた。つぎに、このように調製したメタクリル系樹脂組成物を金型に流し込み、７５℃で１時間の条件で硬化させ、成形体を得た。 (Example 3)
75 parts by mass of methyl methacrylate [Chemical Formula 1], 10 parts by mass of isobornyl methacrylate [Chemical Formula 2] as a cyclic methacrylate, 15 parts by mass of polymethyl methacrylate, and trimethylolpropanetri as a polyfunctional unsaturated ester compound 1 part by weight of methacrylate [Chemical Formula 3] and 0.3 part by weight of di- (3,5,5-trimethylhexanoyl) peroxide as a radical polymerization initiator were mixed to obtain a methacrylic resin composition. As the radical polymerization initiator, Trigonox 36-C75 manufactured by Kayaku Akzo Co., Ltd. was used. Next, the methacrylic resin composition thus prepared was poured into a mold and cured at 75 ° C. for 1 hour to obtain a molded body.
　（実施例４）
　メタクリル酸メチルとポリメタクリル酸メチルの配合比率を変えた点を除いては実施例３と同様にして成形した。 Example 4
Molding was performed in the same manner as in Example 3 except that the blending ratio of methyl methacrylate and polymethyl methacrylate was changed.
　（実施例８）
　環状メタクリル酸エステルとしてイソボルニルメタクリレート［化２］１００質量部に、多官能不飽和エステル化合物としてトリメチロールプロパントリメタクリレート［化３］１質量部と、ラジカル重合開始剤としてジ‐（３，５，５－トリメチルヘキサノイル）パーオキサイド０．３質量部を混合し、メタクリル系樹脂組成物を得た。なお、ラジカル重合開始剤は化薬アクゾ（株）のトリゴノックス３６－Ｃ７５を用いた。つぎに、このように調製したメタクリル系樹脂組成物を金型に流し込み、７５℃で１時間の条件で硬化させ、成形体を得た。 (Example 8)
100 parts by mass of isobornyl methacrylate [Chemical Formula 2] as a cyclic methacrylate, 1 part by mass of trimethylolpropane trimethacrylate [Chemical Formula 3] as a polyfunctional unsaturated ester compound, and di- (3,5 as a radical polymerization initiator , 5-trimethylhexanoyl) peroxide 0.3 parts by mass was mixed to obtain a methacrylic resin composition. As the radical polymerization initiator, Trigonox 36-C75 manufactured by Kayaku Akzo Co., Ltd. was used. Next, the methacrylic resin composition thus prepared was poured into a mold and cured at 75 ° C. for 1 hour to obtain a molded body.
　（実施例９）
　メタクリル酸メチル［化１］９０質量部に、環状メタクリル酸エステルとしてイソボルニルメタクリレート［化２］１０質量部と、ヒンダートペピリジン骨格を有するアクリル酸誘導体又はメタクリル酸誘導体としてメタクリル酸１,２,２,６,６－ペンタメチル－４－ピペリジル［化４］１質量部と、多官能不飽和エステル化合物としてトリメチロールプロパントリメタクリレート［化３］１質量部と、ラジカル重合開始剤としてジ‐（３，５，５－トリメチルヘキサノイル）パーオキサイド０．３質量部を混合し、メタクリル系樹脂組成物を得た。なお、ラジカル重合開始剤には化薬アクゾ（株）のトリゴノックス３６－Ｃ７５を、ヒンダートペピリジン骨格を有するアクリル酸誘導体又はメタクリル酸誘導体には（株）ＡＤＥＫＡ製のＡＤＫ　ＳＴＡＢ　ＬＡ－８２を用いた。つぎに、このように調製したメタクリル系樹脂組成物を金型に流し込み、７５℃で１時間の条件で硬化させ、成形体を得た。 Example 9
90 parts by mass of methyl methacrylate [Chemical Formula 1], 10 parts by mass of isobornyl methacrylate [Chemical Formula 2] as a cyclic methacrylic acid ester, and 1,2 methacrylic acid as an acrylic acid derivative or methacrylic acid derivative having a hindered topepyridine skeleton 1,6,6-pentamethyl-4-piperidyl [Chemical Formula 4] 1 part by mass, polyfunctional unsaturated ester compound trimethylolpropane trimethacrylate [Chemical Formula 3] 1 part by mass, radical polymerization initiator di- (3 , 5,5-trimethylhexanoyl) peroxide 0.3 parts by mass was mixed to obtain a methacrylic resin composition. Trigonox 36-C75 of Kayaku Akzo Co., Ltd. was used as the radical polymerization initiator, and ADK STAB LA-82 manufactured by ADEKA Co., Ltd. was used as the acrylic acid derivative or methacrylic acid derivative having a hindered topepyridine skeleton. . Next, the methacrylic resin composition thus prepared was poured into a mold and cured at 75 ° C. for 1 hour to obtain a molded body.
Figure JPOXMLDOC01-appb-C000004
 　（実施例１０、１１、１６）
　メタクリル酸メチルとヒンダートペピリジン骨格を有するメタクリル酸誘導体の配合比率を変えた点を除いては実施例９と同様にして成形した。
Figure JPOXMLDOC01-appb-C000004
 (Examples 10, 11, and 16)
Molding was carried out in the same manner as in Example 9 except that the blending ratio of methyl methacrylate and a methacrylic acid derivative having a hindered topepyridine skeleton was changed.
　（実施例１２）
　メタクリル酸メチル［化１］９０質量部に、環状メタクリル酸エステルとしてイソボルニルメタクリレート［化２］１０質量部と、紫外線を吸収する官能基を骨格に有するアクリル酸誘導体又はメタクリル酸誘導体として１－（２－ベンゾトリアゾール）－２－ヒドロキシ－５－（２－メタクリロイルオキシエチル）ベンゼン［化５］１質量部と、多官能不飽和エステル化合物としてトリメチロールプロパントリメタクリレート［化３］１質量部と、ラジカル重合開始剤としてジ‐（３，５，５－トリメチルヘキサノイル）パーオキサイド０．３質量部を混合し、メタクリル系樹脂組成物を得た。なお、ラジカル重合開始剤は化薬アクゾ（株）のトリゴノックス３６－Ｃ７５を、紫外線を吸収する官能基を骨格に有するアクリル酸誘導体又はメタクリル酸誘導体には大塚化学（株）製のＲＵＶＡ－９３を用いた。つぎに、このように調製したメタクリル系樹脂組成物を金型に流し込み、７５℃で１時間の条件で硬化させ、成形体を得た。 (Example 12)
90 parts by mass of methyl methacrylate [Chemical Formula 1], 10 parts by mass of isobornyl methacrylate [Chemical Formula 2] as a cyclic methacrylic ester, and 1-acrylic acid derivative or methacrylic acid derivative having a functional group that absorbs ultraviolet rays in the skeleton. 1 part by mass of (2-benzotriazole) -2-hydroxy-5- (2-methacryloyloxyethyl) benzene [Chemical Formula 5] and 1 part by mass of trimethylolpropane trimethacrylate [Chemical Formula 3] as a polyfunctional unsaturated ester compound Then, 0.3 part by mass of di- (3,5,5-trimethylhexanoyl) peroxide as a radical polymerization initiator was mixed to obtain a methacrylic resin composition. The radical polymerization initiator is Trigonox 36-C75 of Kayaku Akzo Co., Ltd., and the acrylic acid derivative or methacrylic acid derivative having a functional group that absorbs ultraviolet rays as a skeleton is RUVA-93 manufactured by Otsuka Chemical Co., Ltd. Using. Next, the methacrylic resin composition thus prepared was poured into a mold and cured at 75 ° C. for 1 hour to obtain a molded body.
Figure JPOXMLDOC01-appb-C000005
 　（実施例１３、１４、１７）
　メタクリル酸メチルと紫外線を吸収する官能基を骨格に有するメタリル酸誘導体の配合比率を変えた点を除いては実施例１２と同様にして成形した。
Figure JPOXMLDOC01-appb-C000005
 (Examples 13, 14, and 17)
Molding was carried out in the same manner as in Example 12 except that the blending ratio of methyl methacrylate and a methallylic acid derivative having a functional group that absorbs ultraviolet rays in the skeleton was changed.
　（実施例１５）
　メタクリル酸メチル［化１］９０質量部に、環状メタクリル酸エステルとしてイソボルニルメタクリレート［化２］１０質量部と、ヒンダートペピリジン骨格を有するアクリル酸誘導体又はメタクリル酸誘導体としてメタクリル酸１,２,２,６,６－ペンタメチル－４－ピペリジル［化４］１質量部と、紫外線を吸収する官能基を骨格に有するアクリル酸誘導体又はメタクリル酸誘導体として１－（２－ベンゾトリアゾール）－２－ヒドロキシ－５－（２－メタクリロイルオキシエチル）ベンゼン［化５］１質量部と、多官能不飽和エステル化合物としてトリメチロールプロパントリメタクリレート［化３］１質量部と、ラジカル重合開始剤としてジ‐（３，５，５－トリメチルヘキサノイル）パーオキサイド０．３質量部を混合し、メタクリル系樹脂組成物を得た。なお、ラジカル重合開始剤には化薬アクゾ（株）のトリゴノックス３６－Ｃ７５を、ヒンダートペピリジン骨格を有するアクリル酸誘導体又はメタクリル酸誘導体には（株）ＡＤＥＫＡ製のＡＤＫ　ＳＴＡＢ　ＬＡ－８２を、紫外線を吸収する官能基を骨格に有するアクリル酸誘導体又はメタクリル酸誘導体には大塚化学（株）製のＲＵＶＡ－９３を用いた。つぎに、このように調製したメタクリル系樹脂組成物を金型に流し込み、７５℃で１時間の条件で硬化させ、成形体を得た。 (Example 15)
90 parts by mass of methyl methacrylate [Chemical Formula 1], 10 parts by mass of isobornyl methacrylate [Chemical Formula 2] as a cyclic methacrylic acid ester, and 1,2 methacrylic acid as an acrylic acid derivative or methacrylic acid derivative having a hindered topepyridine skeleton 1 part of 2,6,6-pentamethyl-4-piperidyl [Chemical Formula 4] and 1- (2-benzotriazole) -2-hydroxy as an acrylic acid derivative or methacrylic acid derivative having a functional group that absorbs ultraviolet rays in the skeleton 1 part by mass of -5- (2-methacryloyloxyethyl) benzene [Chemical Formula 5], 1 part by mass of trimethylolpropane trimethacrylate [Chemical Formula 3] as a polyfunctional unsaturated ester compound, and di- (3 , 5,5-trimethylhexanoyl) peroxide 0.3 parts by mass, A system resin composition was obtained. The radical polymerization initiator is Trigonox 36-C75 manufactured by Kayaku Akzo Co., Ltd., and the acrylic acid derivative or methacrylic acid derivative having a hindered topepyridine skeleton is ADK STAB LA-82 manufactured by ADEKA Co., Ltd. RUVA-93 manufactured by Otsuka Chemical Co., Ltd. was used as an acrylic acid derivative or a methacrylic acid derivative having a functional group that absorbs. Next, the methacrylic resin composition thus prepared was poured into a mold and cured at 75 ° C. for 1 hour to obtain a molded body.
　（比較例１）
　メタクリル酸メチル［化１］１００質量部に、多官能不飽和エステル化合物としてトリメチロールプロパントリメタクリレート［化３］１質量部とラジカル重合開始剤としてジ‐（３，５，５－トリメチルヘキサノイル）パーオキサイド０．３質量部を混合し、メタクリル系樹脂組成物を得た。なお、ラジカル重合開始剤は化薬アクゾ（株）のトリゴノックス３６－Ｃ７５を用いた。つぎに、このように調製したメタクリル系樹脂組成物を金型に流し込み、７５℃で１時間の条件で硬化させ、成形体を得た。 (Comparative Example 1)
100 parts by mass of methyl methacrylate [Chemical Formula 1], 1 part by mass of trimethylolpropane trimethacrylate [Chemical Formula 3] as a polyfunctional unsaturated ester compound and di- (3,5,5-trimethylhexanoyl) as a radical polymerization initiator 0.3 parts by mass of peroxide was mixed to obtain a methacrylic resin composition. As the radical polymerization initiator, Trigonox 36-C75 manufactured by Kayaku Akzo Co., Ltd. was used. Next, the methacrylic resin composition thus prepared was poured into a mold and cured at 75 ° C. for 1 hour to obtain a molded body.
　（比較例２）
　メタクリル酸メチル［化１］９０質量部に、ポリメタクリル酸メチル１０質量部と、多官能不飽和エステル化合物としてトリメチロールプロパントリメタクリレート［化３］１質量部と、ラジカル重合開始剤としてジ‐（３，５，５－トリメチルヘキサノイル）パーオキサイド０．３質量部を混合し、メタクリル系樹脂組成物を得た。なお、ラジカル重合開始剤は化薬アクゾ（株）のトリゴノックス３６－Ｃ７５を用いた。つぎに、このように調製したメタクリル系樹脂組成物を金型に流し込み、７５℃で１時間の条件で硬化させ、成形体を得た。 (Comparative Example 2)
90 parts by mass of methyl methacrylate [Chemical Formula 1], 10 parts by mass of polymethyl methacrylate, 1 part by mass of trimethylolpropane trimethacrylate [Chemical Formula 3] as the polyfunctional unsaturated ester compound, and di- ( 3,5,5-Trimethylhexanoyl) peroxide 0.3 parts by mass was mixed to obtain a methacrylic resin composition. As the radical polymerization initiator, Trigonox 36-C75 manufactured by Kayaku Akzo Co., Ltd. was used. Next, the methacrylic resin composition thus prepared was poured into a mold and cured at 75 ° C. for 1 hour to obtain a molded body.
　〈性能評価〉
　上記のように作製した成形体の外観、透明性、耐熱性及び硬化収縮率の評価を行った。 <Performance evaluation>
The appearance, transparency, heat resistance, and cure shrinkage of the molded body produced as described above were evaluated.
　（１）外観
　成形体の外観は目視で観察し、割れや発泡、白化がないものを「○」、割れや発泡、白化があるものを「×」とした。 (1) Appearance The appearance of the molded product was visually observed, and “o” indicates that there is no cracking, foaming, or whitening, and “x” indicates that there is cracking, foaming, or whitening.
　（２）透明性
　得られた成形体の透明性は、厚み３ｍｍの成形品を用いてＪＩＳ　Ｋ　７１０５に準拠して行った。 (2) Transparency Transparency of the obtained molded body was performed according to JIS K 7105 using a molded product having a thickness of 3 mm.
　（３）耐熱性
　得られた成形品の耐熱性は、ガラス転移温度により評価を行った。ガラス転移温度の測定はＪＩＳ　Ｋ　７１２１に準拠して行った。 (3) Heat resistance The heat resistance of the obtained molded product was evaluated by the glass transition temperature. The glass transition temperature was measured according to JIS K7121.
　（４）硬化収縮率
　得られた成形品の硬化収縮率は、ＪＩＳ　Ｋ　６９０１に準拠して測定した。 (4) Curing Shrinkage The curing shrinkage of the obtained molded product was measured according to JIS K 6901.
　（５）耐候性
　耐候性試験は，スガ試験機製のＤＰＷＬ－５Ｒを用いて行った。試験条件としてはＪＩＳ　Ａ　１４１５およびＪＩＳ　Ｋ　７３５０－３に基づいて行った。６つのサンプルをデューパネルウェザーメータに設置した後，ブラックパネル温度を６３℃（照射時）、放射照度を３０Ｗ／ｍ2（３００～４００ｎｍ）に設定して照射４時間，消灯（結露）４時間の試験サイクルで２００時間行った。評価方法としては、樹脂の裏面に白板を配置して色差計で測定を行い試験前後の色の変化をΔＥ値で示した。 (5) Weather resistance The weather resistance test was conducted using DPWL-5R manufactured by Suga Test Instruments. The test conditions were based on JIS A 1415 and JIS K 7350-3. After six samples were installed in a dew panel weather meter, the black panel temperature was set to 63 ° C (during irradiation), the irradiance was set to 30 W / m 2 (300 to 400 nm), irradiation for 4 hours, and extinction (condensation) for 4 hours. The test cycle was 200 hours. As an evaluation method, a white plate was placed on the back surface of the resin and measured with a color difference meter, and the change in color before and after the test was shown as a ΔE value.
Figure JPOXMLDOC01-appb-T000006
 　表１から明らかなように、実施例１～８は比較例１、２と対比して、透明性が同等で、耐熱性に優れ、硬化収縮が抑えられている。実施例９～１５においては、更に耐候性に優れている。このことから、メタクリル系樹脂組成物に環状メタクリル酸エステルを配合すると、耐熱性及び透明性を維持したまま硬化収縮を低減することができる。更に、ヒンダートピペリジン骨格を有するものと、紫外線を吸収する官能基を骨格に有するものの、どちらか一方若しくは両方を、上記メタクリル系樹脂組成物に配合すると、成形体の耐候性を向上させることができる。また、実施例１６、１７のように、ヒンダートピペリジン骨格を有するメタクリル酸誘導体や紫外線を吸収する官能基を骨格に有するメタクリル酸誘導体をメタクリル系樹脂組成物に多く配合すると、成形体の耐熱性又は透明性が低下する傾向にある。
Figure JPOXMLDOC01-appb-T000006
 As is apparent from Table 1, Examples 1 to 8 have the same transparency, excellent heat resistance, and suppressed curing shrinkage, as compared with Comparative Examples 1 and 2. In Examples 9 to 15, the weather resistance is further excellent. From this, when a cyclic methacrylic ester is blended with a methacrylic resin composition, curing shrinkage can be reduced while maintaining heat resistance and transparency. Furthermore, when one or both of the hindered piperidine skeleton and the functional group that absorbs ultraviolet rays are included in the skeleton, the weather resistance of the molded article can be improved. it can. In addition, when a large amount of a methacrylic acid derivative having a hindered piperidine skeleton or a methacrylic acid derivative having a functional group that absorbs ultraviolet rays in the skeleton is blended in the methacrylic resin composition, as in Examples 16 and 17, the heat resistance of the molded body. Or, the transparency tends to decrease.

Claims (7)

  1. 　少なくとも一種類の環状メタクリル酸エステルを含むメタクリル酸エステル化合物と、多官能不飽和エステル化合物と、１０時間半減期温度が５０～１００℃であるラジカル重合開始剤とを含有して成ることを特徴とするメタクリル系樹脂組成物。 A methacrylic acid ester compound containing at least one cyclic methacrylic acid ester, a polyfunctional unsaturated ester compound, and a radical polymerization initiator having a 10-hour half-life temperature of 50 to 100 ° C. A methacrylic resin composition.
  2. 　環状メタクリル酸エステルの比率がメタクリル酸エステル化合物の全量に対して５～４０質量％であることを特徴とする請求項１に記載のメタクリル系樹脂組成物。 The methacrylic resin composition according to claim 1, wherein the ratio of the cyclic methacrylic acid ester is 5 to 40% by mass with respect to the total amount of the methacrylic acid ester compound.
  3. 　アクリル樹脂又はメタクリル樹脂を溶解して含有することを特徴とする請求項１又は２に記載のメタクリル系樹脂組成物。 The methacrylic resin composition according to claim 1, wherein the acrylic resin or methacrylic resin is dissolved and contained.
  4. 　ヒンダートペピリジン骨格を有するアクリル酸誘導体又はメタクリル酸誘導体を前記メタクリル酸エステル化合物の全量に対して０．１以上１０％以下含有することを特徴とする請求項１乃至３のいずれかに記載のメタクリル系樹脂組成物。 The acrylic acid derivative or methacrylic acid derivative having a hindered topepyridine skeleton is contained in an amount of 0.1 to 10% with respect to the total amount of the methacrylic acid ester compound. -Based resin composition.
  5. 　紫外線を吸収する官能基を骨格に有するアクリル酸誘導体又はメタクリル酸誘導体を前記メタクリル酸エステル化合物の全量に対して０．１以上１０％以下含有することを特徴とする請求項１乃至４のいずれかに記載のメタクリル系樹脂組成物。 The acrylic acid derivative or the methacrylic acid derivative having a functional group that absorbs ultraviolet rays in the skeleton is contained in an amount of 0.1 to 10% with respect to the total amount of the methacrylic acid ester compound. The methacrylic resin composition described in 1.
  6. 　請求項１～５のいずれか一項に記載のメタクリル系樹脂組成物を成形して成ることを特徴とする成形体。 A molded article obtained by molding the methacrylic resin composition according to any one of claims 1 to 5.
  7. 　環状メタクリル酸エステルを５～４０質量％含有して成ることを特徴とする請求項６に記載の成形体。 7. The molded article according to claim 6, comprising 5 to 40% by mass of cyclic methacrylic acid ester.
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