WO1999036452A1 - Composition de resine acrylique resistante aux chocs, procede de production de ladite composition et article moule - Google Patents

Composition de resine acrylique resistante aux chocs, procede de production de ladite composition et article moule Download PDF

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Publication number
WO1999036452A1
WO1999036452A1 PCT/JP1999/000073 JP9900073W WO9936452A1 WO 1999036452 A1 WO1999036452 A1 WO 1999036452A1 JP 9900073 W JP9900073 W JP 9900073W WO 9936452 A1 WO9936452 A1 WO 9936452A1
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weight
component
acrylic
modified
syrup
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PCT/JP1999/000073
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English (en)
Japanese (ja)
Inventor
Akira Yanagase
Masaharu Fujimoto
Yasuhiko Nabeshima
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Mitsubishi Rayon Co., Ltd.
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Priority claimed from JP00682398A external-priority patent/JP3270734B2/ja
Application filed by Mitsubishi Rayon Co., Ltd. filed Critical Mitsubishi Rayon Co., Ltd.
Publication of WO1999036452A1 publication Critical patent/WO1999036452A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • the present invention relates to a resin composition having excellent weather resistance, impact resistance, and transparency. More specifically, the present invention relates to an acrylic resin composition containing a modified acrylyl elastomer having excellent weather resistance, impact resistance, transparency, and flexibility, a method for producing the same, and a molded article comprising the resin composition. The present invention also relates to a polyurethane-containing acrylic resin composition having excellent weather resistance, impact resistance, transparency, elongation, and heat deformation resistance, a method for producing the same, and a molded article comprising the resin composition.
  • Background art is relates to a resin composition having excellent weather resistance, impact resistance, and transparency. More specifically, the present invention relates to an acrylic resin composition containing a modified acrylyl elastomer having excellent weather resistance, impact resistance, transparency, and flexibility, a method for producing the same, and a molded article comprising the resin composition.
  • the present invention also relates to a polyurethane-containing acrylic resin composition having excellent weather resistance, impact resistance, transparency,
  • An acryl resin represented by polymethyl methacrylate is a molding material having excellent transparency and weather resistance and a beautiful appearance, but has a drawback of low impact resistance.
  • a method of blending a gen-based rubber containing butadiene as a main component has conventionally been adopted.Blended products obtained by such a method have high impact strength, but rubber. It is known that weather resistance and heat resistance deteriorate due to the residual double bond based on butadiene as a component.
  • polyurethane is a material whose physical properties can be varied widely from hard to soft by selecting the raw materials to be used. Also, when a material having a polymer segment having a glass transition temperature of room temperature or lower, such as poly (tetramethylene oxide) diol or poly ( ⁇ -force prolactone) diol, is used as the raw material polyol component. Is known to be able to obtain an excellent polyurethane rubber with high elasticity and elasticity and excellent durability and abrasion resistance. This rubber is a rubber source that is effective for improving the impact resistance of ataryl resin. It can be.
  • Japanese Patent Publication No. 48-42956 discloses a syrup-like mixture comprising a monomer component having methyl methacrylate as a main component and a polyurethane having alkenyl groups bonded to both ends of the polyurethane.
  • a method for producing an acrylic resin plate having excellent impact resistance by radical polymerization has been proposed. This method also suggests the possibility of application to the field of liquid resin represented by unsaturated polyester resin and epoxy resin of acryl-based syrup containing polyurethane.
  • the cured products obtained from unsaturated polyester resins and epoxy resins generally have the disadvantage of being brittle, the syrup-like materials used in this method provide cured products with excellent impact resistance. It is considered to be a very special liquid resin.
  • a low molecular weight crosslinking agent and a chain transfer agent such as mercaptan are added to a polyurethane-containing syrup, or a low molecular weight crosslinking agent is added to a prepolymerized polyurethane-containing syrup.
  • a chain transfer agent such as mercaptan
  • Attempts to improve the performance of acryl-based rubber include forming a layer of a rubber-like polymer containing acrylate as the main component on the outside of a hard polymer such as alkyl methacrylate, and further forming an alkyl methacrylate on the outside. It has been proposed to blend a graft polymer having a three-layer structure of hard polymer-rubber polymer-hard polymer, onto which a hard polymer component such as an ester is grafted (Japanese Patent Publication No. 48-5). 5 2 3 3 public announcement). According to this method, the impact resistance is improved while maintaining the excellent gloss and transparency of the acrylic resin in a wide temperature range from a low temperature to a high temperature, but the impact resistance cannot be said to be more than + min.
  • polyurethane is an effective rubber source for improving the impact resistance of a cured product of an acryl-based liquid syrup, but the obtained cured product still has satisfactory impact resistance. It has not reached the level it should be.
  • the viscosity of the polyurethane-containing acrylic syrup (polyurethane content: 15%) in these publications is as low as about 50 to 10 O cps (25 ° C). The molecular weight of the body is quite small.
  • An object of the present invention is to provide a modified acrylic elastomer-containing acrylic resin composition having excellent weather resistance, impact resistance, transparency, and flexibility, a method for producing the same, and a molded article comprising the resin composition. is there.
  • Another object of the present invention is to provide a polyurethane-containing acrylic resin composition which is excellent in transparency and has significantly improved impact resistance and tensile elongation, a method for producing the same, and a molded article comprising the resin composition. Is to do.
  • a microparticle in which a specific modified acrylic elastomer is used as an elastomer source, and particles of an acryl polymer (B) containing methyl methacrylate as a main component are dispersed in a continuous phase derived from the modified acrylic elastomer (A).
  • the present invention has been achieved by synthesizing a resin composition having a phase separation structure and a molded article.
  • the present inventors have paid attention to the molecular weight of polyurethane, and have found that by using a high-molecular-weight modified polyurethane copolymerizable with an acrylic monomer, the cured product exhibits a phase-separated structure.
  • the inventors have succeeded in forming a morphology having a microphase-separated structure (elastomer-matrix structure) in which acryl polymer particles are dispersed in a continuous phase of an elastomer composed of a polyurethane component, and have reached the present invention.
  • the gist of the present invention is to provide a modified acrylic elastomer having an alkenyl group in a polymer chain (a) 5 to 50% by weight, and an acrylic monomer (b) containing 50% by weight or more of methyl methacrylate
  • An acrylic syrup composed of 50 to 95% by weight is polymerized and cured by a radical polymerization method.
  • the gist of the present invention consists of a modified polyurethane component (D) of 5 to 50% by weight and an acryl-based polymer component (B) of 50 to 95% by weight containing methyl methacrylate unit of 50% by weight or more.
  • the gist of the present invention is to provide a modified polyurethane (d) having an alkenyl group at the terminal of a polymer chain having a weight average molecular weight of 100,000 or more, 5 to 50% by weight, and 50% by weight or more of methyl methacrylate.
  • FIG. 1 is a photograph of the formed plate obtained in Example 8 taken with a transmission electron microscope.
  • FIG. 2 is a view simulating a transmission electron microscope observation result of the formed plate obtained in Example 8.
  • the modified acrylic elastomer one component (A) constituting the resin composition of the present invention is a component derived from the modified acrylyl elastomer (a) having an alkenyl group in a polymer chain used as a raw material, At least a portion of the alkenyl groups present in the acrylic elastomer (a) are chemically bonded to the polymerizable unsaturated bond groups present in the acrylic monomer (b), which is the raw material of the acrylic polymer component (B). are doing.
  • the acrylic polymer component (B) contains 50 weight parts of methyl methacrylate units. / 0 or less It is a component composed of the above-mentioned polymer, and is a remaining main component excluding the component (A) from the resin composition of the present invention.
  • This resin composition has a microphase separation structure in which particles of a component (B) having a particle diameter of about 0.01 to 10 // m are dispersed in a component (A) forming a continuous phase. .
  • the particle size of the component (B) may be uniform or non-uniform. As the particle diameter is non-uniform and the particle size distribution is larger, the amount of the component (B) particles present in the resin composition can be increased, for example, about 80 to 95% by weight.
  • the amount of the component (B) particles in the resin a component is increased. be able to.
  • a typical chemical bond structure is a crosslinked structure in which the polymer chain of component (A) and the polymer chain of component (B) are crosslinked.
  • the resin composition of the present invention is, for example, a modified acryl elastomer having an alkenyl group in a polymer chain ( a ) (hereinafter referred to as “modified acryl elastomer ( a )”).
  • Modified acrylyl elastomer (a) which is a raw material of the modified acrylyl elastomer component (A), is a polymer containing an alkenyl group in a side chain or a molecular terminal and mainly containing acrylate or methacrylate. It is preferred that Since this alkenyl group can be copolymerized with methyl methacrylate, modified acryl Since a block or a graphitic polymer of the elastomer component (A) and the acrylic polymer component (B) is formed, the interface strength is improved and a tough resin or composition can be obtained.
  • modified acrylic elastomer (a) may be dissolved in an acryl-based monomer (b) mainly composed of methyl methacrylate to obtain a syrup, regardless of its chemical structure.
  • Typical forms are linear, comb-like, and lightly cross-linked.
  • the modified acrylic elastomer (a) has a highly crosslinked structure, the viscosity of the acrylic syrup will increase significantly, causing problems in the handling of the acrylic syrup and in forming the morphology of the cured product.
  • the preferred form is a straight or comb-like form that can be easily and uniformly dissolved in the acrylic monomer (b) mainly composed of methyl methacrylate.
  • the use of a highly crosslinked graft rubber such as a core-shell polymer in a small amount so as not to hinder the viscosity of the acrylic syrup and the formation of the morphology of the cured product is not possible. It can be an effective means for improving the impact resistance of objects.
  • the glass transition temperature T g of the modified acrylic elastomer (a) is preferably 25 ° C. or less. If the Tg is too high, the effect of improving the impact resistance of the obtained cured product is small.
  • the Tg of the modified acrylic elastomer (a) is more preferably 0 ° C or lower.
  • the modified acrylic elastomer (a) is preferably a high molecular weight substance.
  • the use of a high-molecular-weight modified acryl elastomer is advantageous in forming a microphase-separated structure in which the particles of the acrylic polymer component (B) are dispersed in the continuous phase of the modified acryl elastomer component (A). work.
  • the modified acrylic elastomer component (A) acts as a source of the elastomer in the resin composition
  • the use of the high-molecular-weight modified acrylic elastomer (a) makes the resin composition excellent in impact resistance and flexibility. Is expressed.
  • the preferred modified acrylic elastomer (a) has a weight average molecular weight of 50,000 or more, and more preferably 100,000 or more. At this time, even if the content of the modified acrylic elastomer (a) is small, the cured product exhibits excellent impact resistance.
  • the method for producing the modified acrylic elastomer (a) is usually a polymerization step of an acrylyl elastomer containing acrylate or methacrylate as a monomer main component. It comprises two steps of an addition reaction step of adding a reactive group to the acrylic elastomer.
  • the acrylic elastomer containing acrylate or methacrylate as a monomer main component means an elastomer in which at least 50% by weight or more of the constituent unit of the elastomer is acrylate and Z or a methacrylate monomer.
  • a gen-based rubber typified by polybutadiene is used in combination to improve the impact resistance of a resin composition (and a cured product).
  • a resin composition and a cured product.
  • discoloration of the resin composition and deterioration of quality such as mechanical properties occur.
  • the composition may be colored, and if a large amount of butyl acetate or acrylamide is used, the composition may be damaged. Water resistance may decrease.
  • the modified acrylic elastomer (a) used in the present invention at least 50% by weight of its constituent units must be composed of a monomer of acrylate or methacrylate. It is preferably at least 70% by weight.
  • Examples of the acrylate or methacrylate which is a main constituent unit of the modified acrylic elastomer (a) include, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, butyl acrylate, and 2-ethylenol ethoxylate.
  • methacrylates such as methyl methacrylate, ethyl acrylate, isopropyl methacrylate, butyl methacrylate, lauryl methacrylate, and the like.
  • the modified acrylic elastomer (a) in order to adjust the flow characteristics, viscoelasticity, compatibility with the radical polymerizable compound in the polymerizable acrylic syrup, refractive index, and the like of the modified acrylic elastomer (a), a range of less than 50% by weight, Preferably, other polymerizable unsaturated monomers which can be copolymerized with acrylate or methacrylate in a range of less than 30% by weight can be used. Within this range, the properties as acryl rubber are not significantly impaired.
  • Examples of such a polymerizable unsaturated monomer include aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, benzyl acrylate, and benzyl methacrylate; Monomers having a polar group such as lonitrile, acrylamide and methacrylamide, vinyl monomers such as vinyl chloride, vinylidene chloride, and vinyl acetate, and gen-based monomers such as heptagen can be exemplified. .
  • the refractive index of one component of the modified acrylic elastomer (A) and the refractive index of the acrylic polymer component (B) containing methyl methacrylate as a main component must be matched. Is preferred.
  • the acrylic monomer (b) is methyl methacrylate
  • the refractive index of the acrylic polymer component (B) is 1.492
  • a preferred modified acrylic elastomer (a) is, for example, the combination of butyl Atari rate 7 5-8 5 weight 0/0 and styrene 1 5 to 2 5% by weight and the like.
  • the modified acrylic elastomer (a) used in the present invention can be obtained, for example, by reacting a functional group contained in the acrylic elastomer with a compound having an alkenyl group by reacting with the functional group.
  • the acrylic elastomer used in the synthesis of the modified acrylic elastomer (a) must have, besides the combination of the above-mentioned monomers, a functional group that effectively acts to introduce an alkenyl group as shown below.
  • a functional group that effectively acts to introduce an alkenyl group as shown below.
  • a method for adding a reactive group to such an acrylyl elastomer a conventionally well-known reaction can be used.
  • the first method for synthesizing the modified acrylic elastomer (a) utilizes an esterification reaction.
  • an acrylyl elastomer containing a free carboxyl group and an unsaturated hydroxy compound or unsaturated glycidyl compound are used.
  • a reaction between an acrylyl elastomer having a hydroxyl group or a glycidyl group and an unsaturated rubonic acid compound are used.
  • modified acrylic elastomer obtained by this method examples include acrylic rubber obtained by copolymerizing aryl alcohol, hydroxyshethyl acrylate, hydroxyshethyl methacrylate, glycidyl methacrylate, and the like; There are reactants with unsaturated monobasic acids such as acrylic acid, methacrylic acid, crotonic acid, vinylbenzoic acid, and cinnamic acid.
  • acrylyl elastomer obtained by copolymerizing the above-mentioned unsaturated monobasic acid or unsaturated dibasic acid such as maleic acid, fumaric acid, itaconic acid, maleic anhydride or anhydride thereof, and aryl Unsaturated hydroxy compounds such as alcohol, hydroxyshethyl acrylate and hydroxymethyl methacrylate ⁇ Reaction with unsaturated glycidyl compounds such as glycidyl methacrylate Objects also fall into this example.
  • the second method is a method utilizing a urethane reaction, in which a hydroxy group in an acryl elastomer obtained by copolymerizing an unsaturated hydroxy compound and a hydroxy group in an unsaturated hydroxy compound are respectively converted into a diisocyanate compound. It is obtained by adding an unsaturated group to an acrylic elastomer by bonding through a urethane reaction with an isocyanate group of the formula (1).
  • the diisocyanate compound include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalenediisocyanate, tetramethylene diisocyanate, and isophorone diisocyanate.
  • This reaction of adding an unsaturated group uses a known organic tin compound as a catalyst.
  • a known organic tin compound as a catalyst.
  • the above-described reaction control means such as addition of a polymerization inhibitor.
  • a more preferred third method is a method of reacting an acrylic elastomer obtained by copolymerizing a free hydroxyl compound with a compound having both an isocyanate group and an alkenyl group.
  • an unsaturated hydroxy compound can be reacted with an acrylic elastomer having an isocyanate group introduced therein.
  • Compounds that can be used for this purpose include 12-ethyl methacrylate and methacryloyl isocyanate.
  • a well-known urethane catalyst such as dibutyltin diperylate or triethylamine is added. It is effective to increase the reaction rate.
  • the unsaturated isocyanate compound is used in an amount of 0.1 to 3 moles per mole of free hydroxyl groups in the acrylic elastomer. Let react. The temperature of the reaction at this time proceeds even at room temperature, but is preferably 40 ° C. to 130 ° C.
  • Acrylic elastomer one for the production of modified acrylic elastomer one (a) used in the present invention one selected from at least 5 0 wt 0/0 Akurireto the group ing from methacrylates or more monomers Copolymerizing, if desired, less than 50% by weight of said polymerizable unsaturated monomer and a monomer having a functional group to which said reactive unsaturated group can be added. Obtained by
  • a polyester moiety in the acryl elastomer is hydrolyzed, for example, to form a side chain.
  • a functional group can be introduced into the acrylyl elastomer by using a polymerization initiator or a chain transfer agent having a functional group such as a free radical, a propyloxyl group and a hydroxyl group.
  • the modified acrylic elastomer (a) has at least one alkenyl group
  • the content of the alkenyl group unit in the polymer chain is 0.01 mol% with respect to the total number of moles of the monomers constituting the modified acrylyl elastomer. It is preferably in the range of ⁇ 10 mol%.
  • the content of the alkenyl group unit is 0.01 mole. /. If the amount is smaller, the cured product does not substantially contain an effective amount of unsaturated groups, and the resulting cured product does not substantially show the formation of a cured graft and causes macroscopic phase separation, resulting in a non-uniform product. Low impact resistance and low transparency can be obtained.
  • the alkenyl group unit content exceeds 10 mol%, the cured product obtained therefrom has excellent transparency, but the crosslinking point of the elastomer component (A) in the resin composition is high. Since the intermolecular chains are short, only hard and brittle materials can be obtained. Therefore, the content of the alkenyl group unit of the modified acrylic elastomer (a) is preferably in the range of 0.01 to 10 mol%, more preferably 0.05 to 3 mol. / 0 range.
  • Examples of monomers which can be used as an acrylic monomer (b) in a range of 50% by weight or less with methyl methacrylate include: methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid.
  • Non-crosslinkable monomer having only one alkenyl group in one molecule such as ethyl acid, butyl methacrylate, acrylic acid, methacrylic acid, acrylamide, methacrylamide, attarylolitol, methacrylonitrile, styrene, and polymethylstyrene Body.
  • a crosslinkable monomer having a plurality of alkenyl groups having a relatively low molecular weight may be used in combination with a chain transfer agent typified by mercaptan in an appropriate blend, and the alkenyl group of the modified acrylic elastomer may be used. It is extremely effective in improving the impact resistance, heat deformation resistance, and transparency of the cured product of acryl syrup individually or simultaneously, as with the content of acryl.
  • the behavior of the phase separation between the modified acrylic elastomer component (A) and the formed acrylic polymer component (B), which proceeds during the polymerization and curing process of the syrup depends on the mechanical, thermal, and optical properties of the cured product. It is important to note that the phase separation structure can be controlled by controlling the curing rate by using and using a crosslinkable monomer and a chain transfer agent alone and in combination with the polymerization temperature, as well as the content of the graft-linking agent. This is the fundamental principle of the invention.
  • the morphology of the cured product mainly has a phase-separated structure in which acryl-based polymer particles containing methyl methacrylate as a main component are dispersed in a continuous phase derived from a modified acrylic-based elastomer.
  • the domain size can be controlled from several nm to several ⁇ m.
  • crosslinkable monomer examples include ethylene glycol dimethacrylate and 1,3-butylene glycol dimethacrylate.
  • chain transfer agent examples include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and the like.
  • the modified acrylic elastomer (a) is present in a proportion of 5 to 50% by weight based on all radical polymerizable components. Therefore, the remaining 50 to 95% by weight is a monomer component containing methyl methacrylate as a main component.
  • the content of the modified acrylic elastomer ( a ) is less than 5% by weight, the cured product exhibits impact resistance. If the content is insufficient and exceeds 50% by weight, the viscosity of the liquid syrup increases, and it becomes difficult to handle the liquid syrup.
  • radical initiators with medium to low temperature activity such as 2,2, -azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylnoreronitrile), 2,2 2'-Azobis (4-methoxy-2,4-dimethylvalero nitrinole), 1,1'-Azobis (cyclohexane-1-carbonitrile) and other azo-based initiators, lauroyl peroxide, benzoylper
  • peroxide initiators such as oxide, methylethyl ketone peroxide, diisopropylperoxydicarbonate, and dicyclohexylpropoxydicarbonate, and a mixture of several kinds thereof.
  • Curing using a redox initiator in which a peroxide initiator and a reducing agent are combined is also particularly effective for curing in a short time.
  • a redox initiator in which a peroxide initiator and a reducing agent are combined is also particularly effective for curing in a short time.
  • curing with a combination of benzoyl peroxide and dimethyl aniline, or a combination of methyl ethyl ketone peroxide and cobalt naphthenate is possible.
  • the curing temperature may be appropriately set according to the reactivity of the initiator system used.
  • the curing time of the syrup can vary from minutes to tens of hours.
  • Another modified polyurethane component (D) constituting the resin composition of the present invention is a modified polyurethane component having an alkenyl group at a polymer chain terminal, wherein the alkenyl group portion is a raw material of the acrylic polymer component (B). It is a component derived from the modified polyurethane after chemically bonding to the polymerizable unsaturated bonding group.
  • the modified polyurethane component (D) acts as an elastomer source, and its morphology forms an elastomer matrix structure in which the elastomer component forms a continuous phase.
  • the mechanical properties of the resin composition having such a morphology include the degree of phase separation between the modified polyurethane component (D) forming a continuous phase and the acrylic polymer component (B) forming a dispersed phase, and the degree of continuous phase. Is greatly affected by the weight average molecular weight of the modified polyurethane component (D) that forms the polymer. Therefore, in order to increase the elasticity and elasticity of the resin composition, it is necessary to use a modified polyurethane component (D) having a higher molecular weight and excellent mechanical properties to form a continuous phase and form an acrylic phase. It is desirable that the phase separation structure with the polymer component (B) is sufficiently developed. Therefore, the weight average molecular weight of the modified polyurethane component (D) is It is preferably at least 100,000, and more preferably at least 150,000.
  • Acrylic polymer component (B) is a component made of a polymer containing methyl methacrylate units 5 0 wt% or more, a component that make up a portion excluding the component (D) a resin composition .
  • This resin composition has a microphase-separated structure in which particles of a component (B) having a particle diameter of about + nm to several ⁇ are dispersed in a component (D) forming a continuous phase.
  • the modified polyurethane component (D) and at least a part of the acrylic polymer component (B) are chemically bonded.
  • a typical chemical bond structure is a crosslinked structure in which the polymer chain of the component (B) is bridged by the polymer chain of the component (D).
  • the resin composition of the present invention comprises, for example, 5 to 50% by weight of a modified polyurethane (d) having an average molecular weight of 100,000 or more having an alkenyl group at a terminal of a polymer chain, and 50% by weight.
  • a modified polyurethane (d) having an average molecular weight of 100,000 or more having an alkenyl group at a terminal of a polymer chain, and 50% by weight.
  • Curing polyurethane-containing acryl-based syrup consisting of 50 to 95% by weight hereinafter referred to as "urethane-based syrup” as appropriate
  • urethane-based syrup Curing polyurethane-containing acryl-based syrup consisting of 50 to 95% by weight
  • the modified polyurethane which is a raw material of the modified polyurethane component (D) preferably has an alkenyl group at a polymer chain terminal.
  • Tg glass transition temperature
  • T g is more preferably 0 ° C. or lower, and even more preferably 120 ° C. or lower. When the temperature is lower than 120 ° C., a clearly good impact resistance improving effect can be obtained.
  • the raw materials of the modified polyurethane include 1) an organic polyisocyanate, 2) an organic polyol, and 3) an alkyl group copolymerizable with methyl methacrylate, an isocyanate group, and an active hydrogen atom capable of reacting.
  • Three components of a compound or a compound having an alkenyl group and an isocyanate group copolymerizable with methyl methacrylate are used.
  • organic disocyanate examples include commercially available aliphatic or aromatic organic disocyanates. That is, tolylene diisocyanate, p-phenylene diisocyanate To 4,4'-diphenylenomethanediisocyanate, 1,5-naphthalenediisocyanate, polymethylenepolyphenylpolyisocyanate, xylylenediocyanate, 1,6- Xamethylene diisocyanate, isophorone diisocyanate, 1,4-cyclohexanedicisocyanate, 4,4 dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) Cyclohexane and the like can be used. These can be used alone or in combination of several kinds.
  • the organic polyol it is preferable to use an organic polyol having a polymer segment having a glass transition temperature of 25 ° C. or lower in a molecular structure. Further, the molecular weight of the organic polyol is preferably 500 or more, more preferably 500 to 2000. When such an organic polyol is used, a resin composition having excellent impact resistance and tensile elongation can be obtained.
  • organic polyols can be used. That is, poly (oxyethylene) diol, poly (oxypropylene) diol, poly (oxytetramethylene) diol, (propyleneoxide-tetrahydrofuran copolymer) diol, poly (ethyleneadipate) diol, poly (ethyleneadipate) diol Tetramethylene adipate) diol, (ethylene adipate-propylene adipate copolymer) diol, poly ( £ -prolactone) diol, polybutadiene diol (1,2-adduct is the main component), poly (dimethyl) Siloxane) diols, polycarbonate polyols, polyacryl polyols (where butyl acrylate is a main constituent), and the like. These can be used alone or in combination of several kinds.
  • Polyurethane can be synthesized by a polyaddition reaction between these organic polyisocyanates and organic polyols.
  • the mixing ratio of the organic polyisocyanate and the organic polyol is determined so that the molar ratio of the isocyanate group to the hydroxyl group is in the range of 12 to 2 so that any one of the functional groups is present in a somewhat excessive amount.
  • a more preferable mixing ratio of the organic polyisocyanate and the organic polyol for synthesizing a high-molecular-weight polyurethane is such that the molar ratio of the isocyanate group to the hydroxyl group is 0.8 to 1.2.
  • the weight average molecular weight of the modified polyurethane is preferably 100,000 or more, more preferably 150,000 or more.
  • modified polyurethane component (D) It promotes the phase separation with the cryl polymer component (B), and favors the formation of a microphase-separated structure in which the particles of the acrylic polymer component (B) are dispersed in the continuous phase of the modified polyurethane component (D). .
  • the modified polyurethane component (D) acts as a source of the elastomer, the use of the modified polyurethane having a high molecular weight allows the resin composition to exhibit excellent impact resistance and tensile elongation.
  • the viscosity of the urethane-based syrup is greatly affected by the weight-average molecular weight of the modified polyurethane, although there is some difference depending on the composition.
  • the viscosity of a urethane-based syrup having a polyurethane content of 15% at 25 ° C when the weight-average molecular weight of the polyurethane is about 60,000, the viscosity of the urethane-based syrup is about 100 cps. .
  • the weight average molecular weight is about 100,000 and about 150,000
  • the urethane syrup viscosity is about 15 O cps and about 25 O cps, respectively.
  • the viscosity of the urethane syrup is preferably 15 O cps or more, and more preferably 25 O cps or more. More preferred.
  • the urethane-based syrup viscosity varies significantly depending on the polyurethane concentration.However, when the polyurethane-based syrup viscosity is 5 O cps (25 ° C) or less, sufficient impact resistance cannot be obtained at any polyurethane concentration. Not preferred.
  • the high-molecular-weight modified polyurethane can be synthesized in the presence or absence of a solvent.
  • a non-solvent system the reaction is difficult to control because the exothermic reaction is severe, and side reactions are likely to occur.
  • a step of dissolving a high-molecular-weight modified polyurethane in the monomer can be omitted.
  • water in the solvent may significantly prevent the molecular weight from being increased, and may cause a reduction in the reaction rate.
  • the dehydration purification (drying) method of the solvent a sufficiently effective effect can be obtained by a known dehydration purification method, and examples thereof include a dehydration purification method using molecular sieve. It is effective to carry out the reaction by adding a known catalyst for synthesizing urethane such as dibutyltin diallate and triethylamine in order to increase the reaction rate.
  • the modified polyurethane it is preferable to use a compound having an alkenyl group at a polymer chain terminal. Since this alkenyl group can be copolymerized with methyl methacrylate, when the syrup is cured, the modified polyurethane chemically bonds to the methyl methacrylate unit to form a block between the modified polyurethane component (D) and the acrylic polymer component (B). A polymer is formed, the interface strength between the urethane phase and the acryl phase is improved, and a tough resin composition is obtained.
  • a polyurethane compound having an active hydrogen atom is used.
  • a polyurethane group having a hydroxyl group at the molecular chain end a polyurethane compound having an isocyanate group is used.
  • a polyurethane having an alkenyl group at a molecular chain terminal can be synthesized. Since the total number of molecular chain ends decreases as the molecular weight of the urethane increases, it is preferable to use a dehydrated and purified bull compound to ensure the progress of the reaction.
  • Vinylid conjugates used for such purposes include acrylic acid, methacrylic acid, and acrylic acid) 3-hydroxyl, methacrylic acid / 3-hydroxyl, N-methylol acrylamide, N-methylol methacryl Amides, methacrylic acid) 3-isocyanatoethyl, methacryloyl isocyanate and the like.
  • the molecular structure of the high molecular weight modified polyurethane in the present invention may have a crosslinked structure as long as it is soluble in an acryl-based monomer, but it is linear and has alkenyl groups at both ends. Are preferred. If the molecular chain between cross-linking points of the high molecular weight modified polyurethane is too short, the formation of the Miku Mouth phase separation structure of the cured product will be insufficient, and the cured product may not have excellent impact resistance and improved tensile elongation. There is.
  • the cured product has a developed Miku mouth phase separation structure and has excellent elasticity and elasticity.
  • the urethane syrup of the present invention can be obtained by uniformly mixing the thus obtained modified polyurethane and an acrylic monomer (b) containing 50% by weight or more of methyl methacrylate.
  • Methyl methacrylate as acrylic monomer (b) and 50 weight examples include those described above, maleic anhydride, cyclohexylmaleimide, and the like.
  • the acrylic syrup described in the above can be used in combination with a crosslinkable monomer having a plurality of relatively low-molecular-weight alkenyl groups and a chain transfer agent typified by a mercaptan in an appropriate combination. It is extremely effective as in the case of.
  • the degree of progress of the phase separation between the modified polyurethane and the acrylic polymer which proceeds during the syrup curing process, has a large effect on the mechanical, thermal, and optical properties of the cured product (resin composition).
  • the phase separation structure can be controlled by controlling the molecular weight of the modified polyurethane, the cross-linking monomer and the chain transfer agent alone or in combination, and controlling the curing rate by the polymerization temperature and the like.
  • the polymerization-induced phase separation accompanying the formation of the acrylic polymer is sufficiently developed, and the cured product has excellent impact resistance and tensile elongation, but tends to have reduced rigidity.
  • a chain transfer agent such as mercaptan not only slows down the curing rate, but also reduces the grafting efficiency between the modified urethane and the acryl polymer, causing a remarkable phase separation structure, and the cured product has excellent impact resistance. And elongation at the same time, the stiffness is significantly reduced.
  • a small amount of a crosslinkable monomer in combination with this it becomes possible to develop excellent impact resistance without impairing the rigidity.
  • chain transfer agent and the crosslinking monomer examples include those described above.
  • 100 to 25 parts by weight of the urethane syrup, 0 to 25 parts by weight of a monomer having a plurality of alkenyl groups and a molecular weight of 100 or less, and 0 to 1 part by weight of a chain transfer agent are blended. And a radical polymerization method.
  • the content of the modified polyurethane in the urethane syrup is preferably 5 to 50% by weight.
  • Modified polyurethane content is 5% by weight. When the ratio is less than / 0 , the impact resistance of the cured product is insufficient, and the weight is 50%. If it exceeds / 0 , the viscosity of the syrup will be significant And it becomes difficult to handle as a liquid, and the rigidity of the cured product is significantly impaired.
  • a more preferred modified polyurethane content is 10 to 30% by weight.
  • the opening agent exemplified in the curing of the acryl-based syrup described above it is preferable to use the opening agent exemplified in the curing of the acryl-based syrup described above.
  • the curing temperature may be appropriately set according to the reactivity of the initiator system used. Depending on the choice of the initiator system and the setting of the curing temperature, the curing time of the syrup can vary from minutes to tens of hours.
  • acrylic syrups or urethane syrups may be used alone, but depending on the purpose, fibrous reinforcing materials such as glass fiber, carbon fiber, and aramide fiber, calcium carbonate, aluminum hydroxide, silica, and myriad syrup.
  • fibrous reinforcing materials such as glass fiber, carbon fiber, and aramide fiber, calcium carbonate, aluminum hydroxide, silica, and myriad syrup.
  • Inorganic fillers such as force, monomorillonite, whiskers, etc.
  • interfacial modifiers such as silane-based coupling agents, titanium-based coupling agents, ultraviolet absorbers, hindered amine-based light stabilizers, primary antioxidants, secondary
  • Various materials such as polymer stabilizers such as antioxidants, coloring agents such as dyes and pigments, polymerization inhibitors, viscosity-imparting agents such as aerosil, flame retardants, and mold release agents may be used. It is practical.
  • inorganic filler When the above-mentioned inorganic filler is used, 1 to 90% by weight of inorganic filler (c) is blended with respect to 99 to 10% by weight of acrylic syrup or urethane syrup, and radical polymerization is carried out. Is preferred.
  • the advantage of curing a prepolymerized syrup obtained by polymerizing a part of these syrups is that the desired viscosity can be given to the syrup during the curing process, and the uniformity of various fillers is improved.
  • the use of this method applies molding methods featuring high productivity, such as sheet molding compound molding method and bulk molding compound molding method, to these syrups. It is possible to do. If you want to add viscosity to the syrup or reduce the shrinkage, there is a method in which a resin such as polymethyl methacrylate, MS resin, AS resin, or polystyrene is dissolved in the syrup.
  • a method for curing these syrups a method in which a ⁇ -type polymerization is carried out in a cell composed of a tempered glass plate or a polished metal plate and a gasket made of soft polychlorinated vinyl, and a method in which a continuous plate is produced on a continuous belt, are mentioned.
  • a known molding method such as a gap molding method or a spray-up molding method can be used.
  • a molded article comprising the resin composition obtained by the present invention is excellent not only in impact resistance but also in weather resistance and transparency. Its applications include advertising towers, stand signboards, signboards such as rooftop signboards, showcases, dividers, display supplies such as store displays, fluorescent light covers, mood lighting covers, lamp shades, light ceilings, light walls, Lighting equipment such as chandeliers, interior goods such as pendants and mirrors, doors, dome, safety window glass, partitions, architectural parts such as staircase sidings, balcony sidings, roofs for leisure buildings, aircraft windshields, pilot visors , Motorcycles, motorboat windshields, bus light shields, automobile side visors, rear visors, headlight covers, etc.Transportation related parts, audio / video nameplates, stereo covers, TV protective masks, vending machine and other electronic devices Equipment parts, incubators, medical equipment parts such as X-ray parts, machine covers, total Equipment-related parts such as instrument covers, experimental equipment, rulers, dials, observation windows, etc., optical-related parts such as LCD protective plates and
  • part indicates “weight part”
  • % other than total light transmittance and tensile elongation at break indicates “weight./.”.
  • Each molded plate was dyed by immersing it in a 1% aqueous ruthenium oxide solution at room temperature for 1 mm, then cut with a microtome to a thickness of about 80 nm, and using a transmission electron microscope [JE-100 manufactured by JEOL Ltd.]. CXII].
  • the haze was measured at 0 ° C, 23 ° C, and 70 ° C in accordance with the standard of ASTM D1003.
  • the impact whitening property of the molded plate was evaluated by visually observing the appearance of the plate after the falling weight impact test.
  • the appearance of the formed plate after bending was evaluated by visual inspection after the bending test (ASTMD-790).
  • a reaction vessel equipped with a stirrer and a reflux condenser was charged with 100 parts of the elastomer and 400 parts of methyl methacrylate dehydrated and purified with a molecular sieve (hereinafter, abbreviated as “MMA” as appropriate), and stirred at 60 ° C. Dissolved.
  • MMA molecular sieve
  • 0.2 parts of dibutyltin dilaterate and 0.66 parts of 2-methacryloyloxyshethyl isocyanate (power lens MOI manufactured by Showa Denko) were added, the temperature was raised to 80 ° C, and the mixture was heated with stirring for 45 minutes.
  • the reaction solution was cooled to room temperature to obtain an ataryl-based syrup (1).
  • Acrylic syrups (2) to (4) were obtained in the same manner as in Reference Example 1 except for the following.
  • an acrylyl syrup (5) was obtained in the same manner as in Reference Example 2, except that butyl acrylate styrene (80/20) was replaced with ethyl acrylate.
  • an acrylyl syrup (6) was obtained in the same manner as in Reference Example 2 except that butyl acrylate / styrene (80/20) was replaced with butyl acrylate.
  • an acrylyl syrup (7) was obtained in the same manner as in Reference Example 2, except that butyl acrylate / styrene (80/20) was replaced with 21-ethylhexyl acrylate.
  • the obtained cured product was stained with a stain of an aqueous ruthenium oxide solution, cut, and observed with a transmission electron microscope (JEM-10O Cx II, manufactured by JEOL Ltd.). The results shown in Table 3 were obtained for the morphology of the cured product.
  • MMA 0.05 parts of azobisisobutyronitrile was added and mixed well, followed by degassing under reduced pressure to obtain a syrup for cast polymerization.
  • the resulting syrup for cast polymerization was placed in a sealed glass cell, heated for 3 hours in a water bath at 60 ° C, then for 2 hours in an air bath at 130 ° C, and then cooled to a thickness of 3 mm cured product was obtained.
  • an acrylic syrup (1) was obtained.
  • 150 parts of aluminum hydroxide and 0.05 part of 2,2,1-azobis (2,4-dimethylvaleronitrile) were added, and the mixture was thoroughly stirred.
  • I got The obtained cast polymerization syrup was placed in a closed glass cell, heated in a water bath at 60 ° C for 3 hours, then heated in an air bath at 130 ° C for 2 hours, and then cooled to a thickness of 3 mm. A cured product was obtained.
  • FIG. 1 is a photograph of the formed plate obtained in Example 8 taken with a transmission electron microscope.
  • FIG. 2 is a view simulating a transmission electron microscope observation result of the formed plate obtained in Example 8. Although the continuous phase is actually colored, the illustration of the colored state is omitted in FIG.
  • Poly ( ⁇ -force prolactone) diol (Braxel 220 , molecular weight 2 000, manufactured by Daicel Chemical) 330 g (0.165 mol) in a 3 L content vessel equipped with a stirrer, reflux condenser, and dropping funnel was dissolved in 777 g of methyl methacrylate dehydrated and purified using a molecular sieve, and 0.75 g of dibutyltin dilaurate (hereinafter abbreviated as “DBTL”) was added. After 15 minutes of nitrogen substitution, the temperature was raised to 80 ° C.
  • DBTL dibutyltin dilaurate
  • XDI xylylene diisocyanate
  • MMA dehydrated and purified methyl methacrylate
  • Poly ( ⁇ -force prolactatone) diol (Braxel 220, molecular weight 2000, manufactured by Daicel Chemical) 300 g (0.15 mol) and poly ( ⁇ -force prolactone) trio in the same reaction vessel as in Reference Example 10 1 g (Platacell 320, molecular weight 3 000, manufactured by Daicel Chemical) 6 g (0.002 mol) was dissolved in 300 g of MMA 1 dehydrated and purified by molecular sieve, DBTLO. 75 g was added, and nitrogen replacement was performed for 15 minutes. Thereafter, the temperature was raised to 80 ° C. A mixed solution of 34.6 g (0.184 mol) of XDI and 50 g of dehydrated and purified MMA was added dropwise over 30 minutes with stirring, and the mixture was directly heated and stirred for 45 minutes.
  • This reference example is an additional test of urethane syrup used in Examples 1 to 6 and Comparative Examples 1 to 3 of JP-A-3-54217.
  • AIBN 0.06 parts were added, mixed well, and degassed under reduced pressure to obtain a syrup for cast polymerization.
  • the obtained cast polymerization syrup was placed in a sealed glass cell, heated in a water bath at 60 ° C for 3 hours, then in an air bath at 120 ° C for 2 hours, and then cooled to a thickness of 3 mm.
  • the results in Table 9 were obtained.
  • the cured product had a microphase-separated structure in which particles of polymethyl methacrylate (0.1 to 1 / zm) were dispersed in a continuous phase derived from polyurethane.
  • Example 10 0.06 parts of AIBN, 1.2 parts of ethylene glycol dimethacrylate, and n-octylmer force were applied to a mixture having a urethane content of 15% by weight. 0.12 parts of butane were added, and the other conditions were the same as in Example 10 to obtain a syrup for polymerization and a cured product (Table 9). The progress of the phase separation between the continuous phase and the dispersed phase (0.1 to 1 m) was more remarkable than that of Example 10.
  • Example 10 30 parts of MMA was added to 90 parts of the urethane syrup (2) obtained in Reference Example 11 to dilute the urethane content to 15% by weight. Other conditions were the same as in Example 10 to obtain a syrup for polymerization and a cured product (Table 9). The progress of the phase separation between the continuous phase and the dispersed phase (0.1 to 1 / im) was similar to that of Example 10.
  • Example 12 the urethane-based syrup (3) obtained in Reference Example 3 was used in place of the urethane-based syrup (2), and the other conditions were the same as in Example 12 and the polymerization syrup and the cured product were used. (Table 9). The progress of the phase separation between the continuous phase and the dispersed phase (0.1 to 1 / zm) was less than that of Example 10.
  • Example 13 To 120 parts of the urethane syrup (4) obtained in Reference Example 13, 0.06 parts of AIBN was added and mixed well, followed by defoaming under reduced pressure to obtain a syrup for cast polymerization. Next, a cured product was obtained in the same manner as in Example 10 (Table 9). The impact resistance and tensile elongation were slightly improved by using low molecular weight modified polyurethane. The cured product formed a continuous phase derived from polyurethane, but the progress of microphase separation was insufficient.
  • Comparative Example 6 0.1 part of AIBN was added to 120 parts of urethane syrup (4), and 1.2 parts of ethylene glycol dimethacrylate and 0.1 part of n-octyl mercaptan were added. I did it. The other conditions were the same as in Example 10 to obtain a syrup for polymerization and a cured product (Table 9). The impact resistance and tensile elongation were slightly improved by using low molecular weight modified polyurethane. The cured product formed a microphase-separated structure, and the degree of phase separation between the continuous phase and the dispersed phase (0.1 to 1 m) was more remarkable than that of Comparative Example 6.
  • Urethane-based syrup (1) 150 parts of aluminum hydroxide and 0.05 parts of AIBN were added to 100 parts of the mixture, and the mixture was sufficiently stirred, followed by defoaming under reduced pressure to obtain a syrup for cast polymerization. Next, a cured product was obtained in the same manner as in Example 10 (Table 10). The cured product had a microphase-separated structure, and the degree of phase separation between the continuous phase and the dispersed phase (0.1 to 1 ⁇ ) was almost the same as in Example 10.
  • Example 10 150 parts of aluminum hydroxide and 0.05 part of ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ were added to 100 parts of ⁇ syrup, and the mixture was sufficiently stirred, followed by defoaming under reduced pressure to obtain a syrup for cast polymerization. Then, a cured product was obtained in the same manner as in Example 10 (Table 10). The cured product contained no urethane component, and no phase-separated structure was observed.
  • Example 13 The cured product having a thickness of 3 mm obtained in Example 13 was evaluated for haze temperature dependence, impact whitening property and bending whitening property (Tables 11 and 12).
  • the cured product was cut to a size of 2 m in length and 1 m in width, and fitted into a metal frame for soundproof walls.
  • the surface temperature of the cured product rose to 40 ° C due to direct sunlight, but a soundproof wall with excellent appearance and impact resistance was obtained without an increase in haze.
  • Acrylic (registered trademark) L manufactured by Mitsubishi Rayon Co., Ltd.
  • a thickness of 3 mm was evaluated using a thickness of 3 mm (Tables 11 and 12).
  • the acrylic elastomer-containing acryl resin composition of the present invention is excellent in weather resistance, impact resistance, transparency, and flexibility.
  • the polyurethane-containing acrylic resin composition of the present invention has excellent weather resistance, transparency, and heat deformation resistance, and further has an impact resistance. High tensile strength and elongation. Molded articles made of these resin compositions can be applied to applications requiring more severe weather resistance, transparency, and impact resistance than conventional acrylic polymer materials, especially for signboards and displays. Suitable for supplies, lighting supplies, interior goods, construction parts, transport equipment parts, electronic equipment parts, medical equipment parts, equipment parts, optical parts, transportation parts, aquarium supplies, sanitary goods, and game parts.
  • Phase separation progress The difference in the degree of phase separation between the continuous phase (A) and the dispersed phase (B) is visually evaluated in three stages: large, medium, and small, based on differences in the contrast of TEM photographs
  • Example 8 PMM A in continuous phase of modified acrylyl elastomer 0.2
  • Example 9 Uniform micro phase separation structure with particles dispersed 0.1 Comparative Example 4 Uniform structure
  • Example 10 (1) 91 52. 1 1 7700 2 1

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  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention porte sur une composition résineuse qui présente d'excellentes qualités de résistance aux intempéries, de résistance aux chocs, de transparence, et d'autres propriétés. Cette composition contient 5 à 50 % en poids d'un ingrédient à base d'élastomère acrylique modifié (A) ou d'un ingrédient à base de polyuréthane modifié (D) et 50 à 95 % en poids d'un ingrédient à base de polymère acrylique (B) contenant au moins 50 % en poids d'unités de méthacrylate de méthyle et présentant une microstructure à deux phases. Ladite microstructure comprend une phase continue de l'ingrédient (A) ou de l'ingrédient (D) et des particules de l'ingrédient (B) dispersées dans ladite microstructure et dans laquelle au moins une partie de l'ingrédient (A) ou de l'ingrédient (D) est liée chimiquement à au moins une partie de l'ingrédient (B). L'invention porte en outre sur un article moulé contenant ladite composition résineuse.
PCT/JP1999/000073 1998-01-16 1999-01-13 Composition de resine acrylique resistante aux chocs, procede de production de ladite composition et article moule WO1999036452A1 (fr)

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JP00682398A JP3270734B2 (ja) 1998-01-16 1998-01-16 耐衝撃性アクリル樹脂組成物、その製法及び成形品
JP10/6823 1998-01-16
JP10/124534 1998-05-07
JP12453498 1998-05-07

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57182312A (en) * 1981-04-28 1982-11-10 Ici Ltd Manufacture of plastic formed articles and polymerizable compositions therefor
JPS63286415A (ja) * 1987-05-19 1988-11-24 Showa Highpolymer Co Ltd 注型用樹脂組成物
JPH0273817A (ja) * 1988-09-08 1990-03-13 Nippon Shokubai Kagaku Kogyo Co Ltd 樹脂組成物
JPH0354217A (ja) * 1989-07-24 1991-03-08 Mitsubishi Rayon Co Ltd ポリウレタン配合アクリル系液状レジンの硬化方法並びに硬化物
JPH0625362A (ja) * 1992-05-01 1994-02-01 Takemoto Oil & Fat Co Ltd 重合性液状樹脂組成物及びこれを用いた型内硬化成形物
JPH06234822A (ja) * 1993-02-10 1994-08-23 Mitsubishi Rayon Co Ltd グラフト共重合体の製造方法
JPH06239945A (ja) * 1993-02-12 1994-08-30 Mitsubishi Rayon Co Ltd グラフト共重合体の製造方法
JPH10101749A (ja) * 1996-09-26 1998-04-21 Sekisui Chem Co Ltd ポリメタクリル系樹脂体の製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57182312A (en) * 1981-04-28 1982-11-10 Ici Ltd Manufacture of plastic formed articles and polymerizable compositions therefor
JPS63286415A (ja) * 1987-05-19 1988-11-24 Showa Highpolymer Co Ltd 注型用樹脂組成物
JPH0273817A (ja) * 1988-09-08 1990-03-13 Nippon Shokubai Kagaku Kogyo Co Ltd 樹脂組成物
JPH0354217A (ja) * 1989-07-24 1991-03-08 Mitsubishi Rayon Co Ltd ポリウレタン配合アクリル系液状レジンの硬化方法並びに硬化物
JPH0625362A (ja) * 1992-05-01 1994-02-01 Takemoto Oil & Fat Co Ltd 重合性液状樹脂組成物及びこれを用いた型内硬化成形物
JPH06234822A (ja) * 1993-02-10 1994-08-23 Mitsubishi Rayon Co Ltd グラフト共重合体の製造方法
JPH06239945A (ja) * 1993-02-12 1994-08-30 Mitsubishi Rayon Co Ltd グラフト共重合体の製造方法
JPH10101749A (ja) * 1996-09-26 1998-04-21 Sekisui Chem Co Ltd ポリメタクリル系樹脂体の製造方法

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