CN102918103A - Thermoplastic resin composition for lamp housings, and molded articles - Google Patents

Thermoplastic resin composition for lamp housings, and molded articles Download PDF

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Publication number
CN102918103A
CN102918103A CN2011800263622A CN201180026362A CN102918103A CN 102918103 A CN102918103 A CN 102918103A CN 2011800263622 A CN2011800263622 A CN 2011800263622A CN 201180026362 A CN201180026362 A CN 201180026362A CN 102918103 A CN102918103 A CN 102918103A
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quality
mentioned
compound
methyl
rubber
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CN102918103B (en
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石川浩司
福村忍
岩本聪
永谷悠
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Techno UMG Co Ltd
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TAKANON RESIN CO Ltd
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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
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S41/00—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps
    • F21S41/20—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps characterised by refractors, transparent cover plates, light guides or filters
    • F21S41/28—Cover glass
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S41/00—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps
    • F21S41/50—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps characterised by aesthetic components not otherwise provided for, e.g. decorative trim, partition walls or covers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S43/00—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights
    • F21S43/20—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights characterised by refractors, transparent cover plates, light guides or filters
    • F21S43/26—Refractors, transparent cover plates, light guides or filters not provided in groups F21S43/235 - F21S43/255
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S43/00—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights
    • F21S43/50—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights characterised by aesthetic components not otherwise provided for, e.g. decorative trim, partition walls or covers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Non-Portable Lighting Devices Or Systems Thereof (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The present invention provides a thermoplastic resin composition for lamp housings, which comprises: an acrylic-rubber-reinforced graft resin obtained by polymerizing an aromatic vinyl compound and a vinyl cyanide compound in the presence of an acrylic rubber that has a gel content of 70% by mass or more, a toluene swelling degree of 5.5 to 30 times, a volume-mean particle diameter of 100 to 200nm, and a (volume-mean particle diameter)/(number-mean particle diameter) ratio of less than 1.1; a composite-rubber-reinforced graft resin obtained by polymerizing methyl methacrylate, styrene, acrylonitrile and so on in the presence of a composite rubber that comprises both an organosiloxane-based rubber and a (meth)acrylic (co)polymer rubber; and a maleimide copolymer that comprises 10 to 70% by mass of structural units derived from a maleimide compound.

Description

Lampshade is with thermoplastic resin composition and products formed
Technical field
The present invention relates to lampshade and use the thermoplastic resin composition, the products formed that it gives shock resistance, thermotolerance, molded appearance and deposited property excellence, can obtain with the deposited property of the excellence of other synthetic resins and behind direct evaporation beautiful bright looking.
Background technology
The lamps apparatus for vehicle such as headlight, taillight, stop light generally by resin lens section (below be also referred to as " lamp lens ".) and resin cover section (below be also referred to as " lampshade ".) consist of.And, constituent material as these parts, viewpoint from lightweight, productivity etc., resin lens section has used the transparent resins such as polymethylmethacrylate (PMMA), polycarbonate (PC), and resin cover section has used the resin combination that is combined with tinting material in ABS resin etc.
As the method that engages lamp lens and lampshade, the methods such as the deposited method of vibration, the deposited method of hot plate, Laser cladding are arranged.Wherein, vibrate the vibration that face is exerted pressure and back and forth movement causes that deposited method engages for the wish to 2 resin components, utilize its heat of friction with bonding with the position the resinous principle melting and method that both are engaged, for not needing to heat resin component, can enough utmost point short period of time with the method for the excellence that engages between the resin component.But, in the method, the resin that sometimes produces melting overflow in the outside at junction surface for thread phenomenon (hereinafter referred to as " wire drawing ".)。When this wire drawing is remarkable, can see from the outside by the lamp lens, therefore become bad order.In addition, the problem that also exists this wire drawing not remove by post-treatment.
In the deposited method of vibration, not obvious in order to make wire drawing, the known refraction that the method (with reference to patent documentation 1) of making the shape that the junction surface hides is arranged, utilize light makes the method (with reference to patent documentation 2) that the junction surface can not see etc.But any method is all stipulated the shape of resin component, produces the restriction in the design.
On the other hand, as the deposited resin combination of use of vibration of the generation that be used for to suppress wire drawing, known have contain used with divinyl rubber as the composition (patent documentation 3) of the rubber reinforcement phenylethylene resin series of the rubber of the special construction of core, contain the rubber reinforcement phenylethylene resin series that has used the rubber that is consisted of by divinyl and alkyl acrylate composition (patent documentation 4), use the composition (patent documentation 5) of divinyl rubber enhancing resin and silicon-type rubber reinforced resin etc.But, in these documents, about direct evaporation, do not mention.
In order to improve the brightness of lamps apparatus for vehicle, usually lampshade is supplied in secondary processing such as application, metal evaporation, plating.After secondary processing, in order to obtain the outward appearance of the beauty that application, metal evaporation, plating etc. form, the surface that the surface of the products formed before the secondary processing need to be made the smoothness excellence.In order to make the surface smoothing of the products formed of implementing secondary processing, usually carry out primary coat and process.When products formed has smoothness, can not form undercoat (below be also referred to as " without primary coat ".), directly form metal level etc., can cause the cost of goods.As the formation method of the metal level of the formation of having omitted undercoat, known have so-called " directly (directly) vapour deposition method ", usually is used in recent years.Therefore, the resin combination that require to be used for the formation of lampshade etc. not only suppresses wire drawing, and gives the products formed of smoothness excellence.
On the other hand, as the resin combination that is suitable for direct evaporation, disclose and contained the composition that contains rubber graft copolymer (with reference to patent documentation 6) that to have the rubber polymer grafting of specific size distribution.But said composition can not satisfy the level that requires to high bright property in recent years fully, in addition, and about vibrating the wire drawing outward appearance at deposited junction surface, without any mentioning.
Vibrate the aesthetic appearance that the wire drawing in the deposited method causes as improving, and for the composition of improveing direct evaporation, disclose and contained the rubber that uses specific gel content, rubber mass in the composition is the composition that contains rubber graft copolymer (with reference to patent documentation 7) of specified range, the divinyl rubber that contains specific gel content strengthens the composition (with reference to patent documentation 8) of resin and silicon-type rubber reinforced resin, at length controls the method (with reference to patent documentation 9～11) of the structure of organo-silicone rubber etc. with the silicon-type rubber reinforced resin.And, in order to give shock resistance, the composition (with reference to patent documentation 12) that has used to the silicon-type grafting rubbers on a small quantity the multipolymer of alkyl methacrylate in common acrylic rubber enhancing phenylethylene resin series is disclosed.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 9-63307 communique
Patent documentation 2: Japanese kokai publication hei 10-308104 communique
Patent documentation 3: Japanese kokai publication hei 11-199727 communique
Patent documentation 4: TOHKEMY 2000-302824 communique
Patent documentation 5: TOHKEMY 2002-322340 communique
Patent documentation 6: TOHKEMY 2001-002869 communique
Patent documentation 7: TOHKEMY 2004-182835 communique
Patent documentation 8: TOHKEMY 2004-346189 communique
Patent documentation 9: TOHKEMY 2005-139331 communique
Patent documentation 10: TOHKEMY 2005-139332 communique
Patent documentation 11: TOHKEMY 2006-028393 communique
Patent documentation 12: TOHKEMY 2007-217488 communique
Summary of the invention
The problem that invention will solve
As the resin combination that is used to form lampshade, although strongly expect shock resistance, utilize the bright property after the metalized of direct vapour deposition method and suppress the composition of balance excellence of the generation of the wire drawing of vibration in deposited, not yet obtain sufficient resin combination.
The object of the present invention is to provide lampshade with the thermoplastic resin composition and contain its products formed, described lampshade gives the products formed of shock resistance, thermotolerance and molded appearance excellence with the thermoplastic resin composition, obtain with the deposited property of the excellence of other synthetic resins and behind direct evaporation beautiful bright looking.
Be used for solving the means of problem
The present invention is as described below.
1. lampshade is used the thermoplastic resin composition, it contains: [A] is more than the 70 quality % at gel content, the swelling capacity of toluene is 5.5～30 times, volume average particle size is 100～200nm, and under the existence of the ratio of this volume average particle size and number average bead diameter less than 1.1 acrylic rubber matter polymkeric substance (a1), the ethene base system monomer that will contain aromatic ethenyl compound and vinyl cyanide based compound carries out polymerization and the acrylic rubber matter enhancing by polymer graft resin that obtains, [B] contain organo-siloxane be rubber and have from the compounded rubber (b1) of (being total to) polymer rubber of the structural unit of (methyl) alkyl acrylate in the presence of, the second-order transition temperature that will contain homopolymer surpasses (methyl) acrylic acid alkyl ester compound of 0 ℃, the ethene base system monomer of aromatic ethenyl compound and vinyl cyanide based compound carries out polymerization and the compounded rubber that obtains strengthens graft resin, [C] contains 10～70 quality % from the maleimide based copolymer of the structural unit of maleimide amine compound with respect to the entire infrastructure unit, [D] as required contains from the structural unit of aromatic ethenyl compound and from the structural unit of vinyl cyanide based compound and/or from the structural unit of (methyl) acrylic acid alkyl ester compound and do not contain polymkeric substance from the structural unit of maleimide amine compound, it is characterized in that, be that rubber polymer strengthens graft resin [A] with aforesaid propylene acid, above-mentioned compounded rubber strengthens graft resin [B], the total of above-mentioned maleimide based copolymer [C] and above-mentioned polymkeric substance [D] is made as in the situation of 100 quality %, aforesaid propylene acid be the content of rubber polymer (a1) and above-mentioned compounded rubber (b1) content add up to 8～35 quality %, and will consist of the structural unit that aforesaid propylene acid is rubber polymer enhancing graft resin [A], consist of the structural unit that above-mentioned compounded rubber strengthens graft resin [B], the total that consists of the structural unit of above-mentioned maleimide based copolymer [C] and consist of the structural unit of above-mentioned polymkeric substance [D] is made as in the situation of 100 quality %, is 5～30 quality % from the content of the structural unit of maleimide amine compound.
2. use the thermoplastic resin composition such as above-mentioned 1 described lampshade, wherein, aforesaid propylene acid is that containing of rubber polymer (a1) and above-mentioned compounded rubber (b1) is proportional, is made as in the total with both in the situation of 100 quality %, is respectively 10～95 quality % and 5～90 quality %.
3. use the thermoplastic resin composition such as above-mentioned 1 or 2 described lampshades, wherein, aforesaid propylene acid is that rubber polymer (a1) is the polymkeric substance that obtains by carrying out successively the 1st polymerization process and the 2nd polymerization process, described the 1st polymerization process is in the presence of alkylsulfonate and/or alkyl sulfuric ester salt, will by (methyl) acrylic acid alkyl ester compound (m1-1) 50～100 quality % and can with other compounds (m1-2) 0～50 quality % of this (methyl) acrylic acid alkyl ester compound (m1-1) copolymerization (wherein, (m1-1) and (m1-2) add up to 100 quality %.) monomer (m1) that consists of carries out polymerization in aqueous medium, form the operation of the 1st polymkeric substance, described the 2nd polymerization process is in the presence of above-mentioned the 1st polymkeric substance, in the presence of alkylsulfonate and/or the alkyl sulfuric ester salt or in the presence of non-, will be by (methyl) acrylic acid alkyl ester compound (m2-1) 50～99.99 quality %, have 2 above carbon-to-carbon double bonds polymerizable unsaturated compound (m2-2) 0.01～5 quality % and can with other compounds (m2-3) 0～49.99 quality % of this (methyl) acrylic acid alkyl ester compound (m2-1) and this polymerizable unsaturated compound (m2-2) copolymerization (wherein, (m2-1), (m2-2) and (m2-3) add up to 100 quality %.) monomer (m2) that the consists of operation of in aqueous medium, carrying out polymerization; The ratio of above-mentioned monomer (m1) and usage quantity (m2) is made as in the total with both in the situation of 100 quality %, is respectively 1～50 quality % and 50～99 quality %.
As above-mentioned 1～3 in each described lampshade use the thermoplastic resin composition, it mixes the raw material that comprises following component and obtains: [S] contain aforesaid propylene acid be rubber polymer (a1) in the presence of, to not contain the maleimide amine compound, the ethene base system monomer that comprises aromatic ethenyl compound and vinyl cyanide based compound carries out polymerization and the rubber reinforced resin of the acrylic rubber matter enhancing by polymer graft resin that obtains, [T] contains in the presence of above-mentioned compounded rubber (b1), the second-order transition temperature of homopolymer is carried out polymerization above (methyl) acrylic acid alkyl ester compound of 0 ℃, then will not contain the maleimide amine compound, the ethene base system monomer that comprises aromatic ethenyl compound and vinyl cyanide based compound carries out polymerization and the compounded rubber that obtains strengthens the rubber reinforced resin of graft resin, and [U] contains 10～70 quality % from the maleimide based copolymer of the structural unit of maleimide amine compound with respect to the entire infrastructure unit.
5. each described lampshade is used the thermoplastic resin composition as in above-mentioned 1～4, wherein, above-mentioned lampshade be impregnated in the acetone with the thermoplastic resin composition and the limiting viscosity of the acetone soluble polymer that obtains is 0.2～1.0dl/g.
6. each described lampshade use the thermoplastic resin composition as in above-mentioned 1～5, and it is for by the molding material of direct evaporation at the products formed of its surface formation evaporation layer.
7. each described lampshade use the thermoplastic resin composition as in above-mentioned 1～6, and it is the applicable molding material that vibrates the products formed of deposited method.
8. products formed is characterized in that, contains in above-mentioned 1～7 each described lampshade and uses the thermoplastic resin composition.
The effect of invention
Lampshade according to the present invention is used the thermoplastic resin composition, can access the excellent products formed of shock resistance, thermotolerance, molded appearance and deposited property (especially vibrating deposited).And, can access with the deposited property of the excellence of other synthetic resins and behind direct evaporation beautiful bright looking.
Description of drawings
Fig. 1 is that expression is for the general perspective of the resin lens section (lamp lens) of the evaluation of the deposited property of vibration of embodiment.
Fig. 2 is that expression is for the general perspective of the resin cover section (lampshade) of the evaluation of the deposited property of vibration of embodiment.
Fig. 3 is the summary section of the melt-coating part of the resin lens section (lamp lens) of evaluation of the expression deposited property of vibration that is used for embodiment and resin cover section (lampshade).
Embodiment
Below, the present invention is described in detail.
In this manual, " (methyl) vinylformic acid " refers to vinylformic acid and methacrylic acid, and " (being total to) polymkeric substance " refers to homopolymer and multipolymer.
Lampshade of the present invention is characterised in that with the thermoplastic resin composition, contains: [A] at gel content is more than the 70 quality %, the swelling capacity of toluene is (hereinafter referred to as " toluene swell degree ".) be that 5.5～30 times, volume average particle size are under the existence of ratio less than 1.1 acrylic rubber matter polymkeric substance (a1) of 100～200nm and this volume average particle size and number average bead diameter, will contain aromatic ethenyl compound and vinyl cyanide based compound ethene base system monomer (below be also referred to as " ethene base system monomer (a2) ".) carry out polymerization and the acrylic rubber matter enhancing by polymer graft resin that obtains (below be also referred to as " composition [A] ".), [B] contain organo-siloxane be rubber and have from the compounded rubber (b1) of (being total to) polymer rubber of the structural unit of (methyl) alkyl acrylate in the presence of, the ethene base system monomer that the second-order transition temperature that will contain homopolymer surpasses 0 ℃ (methyl) acrylic acid alkyl ester compound, aromatic ethenyl compound and vinyl cyanide based compound carry out polymerization and the compounded rubber that obtains strengthen graft resin (below be also referred to as " composition [B] ".), [C] with respect to the entire infrastructure unit contain 10～70 quality % from the maleimide based copolymer of the structural unit of maleimide amine compound (below be also referred to as " composition [C] ".), [D] as required contain the structural unit that is selected from from aromatic ethenyl compound, from the structural unit of vinyl cyanide based compound and from least a kind of structural unit in the structural unit of (methyl) acrylic acid alkyl ester compound, and do not contain polymkeric substance from the structural unit of maleimide amine compound (below be also referred to as " composition [D] ".), with mentioned component [A], mentioned component [B], the total of mentioned component [C] and mentioned component [D] is made as in the situation of 100 quality %, aforesaid propylene acid be the content of rubber polymer (a1) and above-mentioned compounded rubber (b1) content add up to 8～35 quality %, and at the structural unit that will consist of mentioned component [A], consist of the structural unit of mentioned component [B], the total that consists of the structural unit of mentioned component [C] and consist of the structural unit of mentioned component [D] is made as in the situation of 100 quality %, is 5～30 quality % from the content of the structural unit of maleimide amine compound.
Mentioned component [A] for by in aforesaid propylene acid be rubber polymer (a1) in the presence of ethene base system monomer (a2) is carried out polymerization (hereinafter referred to as " graft polymerization ".) and the resin combination that obtains (hereinafter referred to as " rubber reinforced resin ".) in contained acrylic rubber matter enhancing by polymer graft resin.The copolymer grafted that this acrylic rubber matter enhancing by polymer graft resin is ethene base system monomer (a2) is in the resin of acrylic rubber matter polymkeric substance (a1), by acrylic rubber matter polymkeric substance section and the multipolymer section formation that comprises from the structural unit of ethene base system monomer (a2).
In addition, the rubber reinforced resin that obtains by graft polymerization usually except rubber polymer strengthens graft resin, comprise with rubber polymer not (being total to) polymkeric substance of grafting (hereinafter referred to as " not graftomer ".)。This not the formation of graftomer depend on the kind of the ethene base system monomer (a2) of use, above-mentioned ethene base system monomer (a2) contains in the situation of maleimide amine compound, and the not graftomer that obtains is included in composition of the present invention in the composition [C] usually.In addition, above-mentioned ethene base system monomer (a2) contains in the situation of other aromatic ethenyl compounds except the maleimide amine compound and vinyl cyanide based compound and/or (methyl) acrylic acid alkyl ester compound, and the not graftomer that obtains is included in composition of the present invention in the composition [D] usually.
Aforesaid propylene acid is that rubber polymer (a1) is that gel content is that 70 quality % are above, the toluene swell degree is that 5.5～30 times, volume average particle size are that the ratio of 100～200nm and volume average particle size and number average bead diameter is less than 1.1 polymkeric substance (acrylic rubber).And this acrylic rubber matter polymkeric substance (a1) is generally to have the polymkeric substance section contained from the structural unit of (methyl) acrylic acid alkyl ester compound, is (being total to) polymkeric substance of rubber mass down at 25 ℃.
Aforesaid propylene acid is that rubber polymer (a1) can be for containing the homopolymer from the structural unit of (methyl) acrylic acid alkyl ester compound, also can be for containing the multipolymer of this structural unit.This multipolymer can be for containing more than 2 kinds the multipolymer from the structural unit of (methyl) acrylic acid alkyl ester compound, also can be for containing from the structural unit of (methyl) acrylic acid alkyl ester compound with from the multipolymer of the structural unit of other ethene base system monomers.And this acrylic rubber matter polymkeric substance (a1) can be cross-linked polymer, also can be non-cross-linked polymer.
Acid is rubber polymer (a1) as the formation aforesaid propylene, be used for (methyl) acrylic acid alkyl ester compound from the formation of the structural unit of (methyl) acrylic acid alkyl ester compound, can enumerate: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) 2-EHA, (methyl) Octyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) cyclohexyl acrylate etc.These compounds can be used singly or in combination more than 2 kinds.In addition, wherein, the carbonatoms of the alkyl of preferred ester section is 1～14 compound, particularly preferably n-butyl acrylate and 2-EHA.
In addition, aforesaid propylene acid is that rubber polymer (a1) is in the situation of multipolymer, the compound (ethene base system monomer) that is used for the formation of other structural units, except (methyl) acrylic acid alkyl ester compound, can be the compound with 1 carbon-to-carbon double bond and/or the compound with 2 above carbon-to-carbon double bonds.
As the compound with 1 carbon-to-carbon double bond, can enumerate: aromatic ethenyl compound, vinyl cyanide based compound, contain amido unsaturated compound, alkyl vinyl ether, vinylidene chloride etc.In addition, these compounds may be used singly or in combination of two or more.
As above-mentioned aromatic ethenyl compound, can enumerate: vinylbenzene, p-methylstyrene, o-methyl styrene, a vinyl toluene, ethyl styrene, t-butyl styrene, alpha-methyl styrene, 1,1-diphenyl benzene ethene, N, N-diethyl-p-aminophenyl ethene, N, the N-diethyl-to amino methyl vinylbenzene, vinyl pyridine, vinyl-dimethyl benzene, monochloro vinylbenzene, dichlorostyrene, single bromstyrol, Dowspray 9, phenylstilbene bromide, fluorobenzene ethene, vinyl naphthalene etc.
As above-mentioned vinyl cyanide based compound, can enumerate: vinyl cyanide, methacrylonitrile etc.
As the above-mentioned amido unsaturated compound that contains, can enumerate: acrylamide, Methacrylamide etc.
As the abovementioned alkyl vinyl ether, the carbonatoms that can enumerate the alkyl that consists of alkyl section is 1～6 compound.
In addition, as the compound with 2 above carbon-to-carbon double bonds, can enumerate: (methyl) acrylate of 2 functionality aromatic ethenyl compounds, 2 functionalities (methyl) acrylate, 3 functionalities (methyl) acrylate, 4 functionalities (methyl) acrylate, 5 functionalities (methyl) acrylate, 6 functionalities (methyl) acrylate, polyvalent alcohol etc.In addition, these compounds may be used singly or in combination of two or more.
As above-mentioned 2 functionality aromatic ethenyl compounds, can enumerate: Vinylstyrene, divinyl toluene etc.
As above-mentioned 2 functionalities (methyl) acrylate, can enumerate: 1,6 hexanediol diacrylate, ethylene glycol dimethacrylate, neopentylglycol diacrylate, (methyl) allyl acrylate, neopentylglycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate etc.
As above-mentioned 3 functionalities (methyl) acrylate, can enumerate: Viscoat 295, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl etc.
As above-mentioned 4 functionalities (methyl) acrylate, can enumerate: tetramethylol methane tetraacrylate, pentaerythritol tetramethylacrylate etc.
As above-mentioned 5 functionalities (methyl) acrylate, can enumerate: tetramethylolmethane five acrylate, tetramethylolmethane pentamethyl-acrylate etc.
As above-mentioned 6 functionalities (methyl) acrylate, can enumerate: dipentaerythritol six acrylate, dipentaerythritol hexamethyl acrylate etc.
As (methyl) acrylate of above-mentioned polyvalent alcohol, can enumerate: (gathering) ethylene glycol dimethacrylate etc.
In addition, can use two (acryloxy ethyl) ethers etc. of diallyl maleate, diallyl fumarate, triallyl cyanurate, triallyl isocyanurate, Phthalic acid, diallyl ester, dihydroxyphenyl propane.
Wherein, preferable methyl allyl acrylate and triallyl cyanurate.
Acid is rubber polymer (a1) as aforesaid propylene, preferably contains the multipolymer from the structural unit of (methyl) acrylic acid alkyl ester compound.In this case, when the total amount that consists of whole structural unit of multipolymer is made as 100 quality %, content from the structural unit of (methyl) acrylic acid alkyl ester compound is preferably 50～100 quality %, more preferably 70～100 quality %, more preferably 80～100 quality %.
Aforesaid propylene acid is that the gel content of rubber polymer (a1) and the kind of structural unit have nothing to do, and is more than the 70 quality %, is preferably more than the 75 quality %, more preferably more than the 80 quality %.When using the high acrylic rubber matter polymkeric substance (a1) of gel content, be equipped with on the surface of the products formed that obtains in the situation of metal level etc., can access excellent bright property.
In addition, aforesaid propylene acid is that the toluene swell degree of rubber polymer (a1) and the kind of structural unit have nothing to do, and is 5.5～30 times, is preferably 6～25 times, more preferably 10～23 times.When using the acrylic rubber matter polymkeric substance (a1) of above-mentioned scope, can access the products formed of shock resistance excellence, be equipped with on the surface of the products formed that obtains in the situation of metal level etc., can access excellent bright property.
In addition, above-mentioned gel content and toluene swell degree can utilize for example following method to obtain.
Approximately 0.2 gram of at first, weighing acrylic rubber matter polymkeric substance (a1) (is designated as Wr with quality.), drop among the toluene 25ml, stir lightly.25 ℃ lower place 48 hour, use 200 purpose wire nettings of in advance weighing (quality be designated as Wm gram thereafter.) filter, be separated into insoluble minute and solvable minute.After the separation, rapidly with the wire netting weighing with filtering separation in insoluble minute (quality is designated as the W1 gram), deduct the weighing value (Wm) of wire netting from this weighing value (W1), insoluble minute the weighing value that obtains with toluene swell (is designated as the Ws gram with quality.)。Secondly owing to containing toluene with in insoluble minute of toluene swell, therefore, with its 25 ℃ lower air-dry 12 hours, then use Vacuumdrier 60 ℃ of lower dryings 12 hours, thus contained toluene drying in insoluble minute is removed.(quality was designated as the W2 gram with dried insoluble minute with the wire netting weighing.), deducting the weighing value (Wm) of wire netting from this weighing value (W2), the dry weight that obtains insoluble minute (is designated as the Wd gram with quality.)。Utilize following formula to calculate gel content and toluene swell degree by these weighing values.
Gel content (quality %)=[Wd (g)/Wr (g)] * 100
＝[{W2(g)-Wm(g)}/Wr(g)]×100
Toluene swell degree (doubly)=Ws (g)/Wd (g)
＝[W1(g)-Wm(g)]/[W2(g)-Wm(g)]
The kind of the kind of the monomer that uses when in addition, above-mentioned gel content and toluene swell degree are made acrylic rubber matter polymkeric substance (a1) by suitably being chosen in and amount thereof, chain-transfer agent (molecular weight regulator) and amount thereof, polymerization time, polymerization temperature, polymerisation conversion etc. are adjusted.
From the shock resistance of products formed and the viewpoint of bright property, aforesaid propylene acid be rubber polymer (a1) volume average particle size (below be also referred to as " Mv ".) be 100～200nm, be preferably 105～180nm, more preferably 110～170nm.
In addition, with the volume average particle size (Mv) of above-mentioned acrylic rubber matter polymkeric substance (a1) and number average bead diameter (below be also referred to as " Mn ".) the size distribution (Mv/Mn) that represents of ratio less than 1.1, preferably less than 1.07.
In above-mentioned extraneous situation, the sometimes shock resistance of products formed, bright property and the inhibition of vibrating the wire drawing when deposited becomes insufficient in above-mentioned Mv and/or size distribution (Mv/Mn).
Aforesaid propylene acid is that the Mv of rubber polymer (a1) and Mn for example can utilize HONEYWELL society system " マ イ Network ロ ト ラ ッ Network UPA150 " (trade(brand)name) to measure.
Aforesaid propylene acid is that rubber polymer (a1) can be the polymkeric substance that utilizes known manufacture method to obtain, and the multipolymer that the manufacture method with the 1st polymerization process and the 2nd polymerization process below particularly preferably utilizing obtains is (hereinafter referred to as " multipolymer (a11) ".)。
(1) the 1st polymerization process
At alkylsulfonate and/or alkyl sulfuric ester salt (following they are also referred to as " emulsifying agent (e) ".) existence under, will by (methyl) acrylic acid alkyl ester compound (m1-1) 50～100 quality % and can with other compounds (m1-2) 0～50 quality % of (methyl) acrylic acid alkyl ester compound (m1-1) copolymerization (wherein, (m1-1) and (m1-2) add up to 100 quality %.) monomer (m1) that consists of carries out polymerization in aqueous medium, form the polymerization process of the 1st polymkeric substance.
(2) the 2nd polymerization process
In the presence of above-mentioned the 1st polymkeric substance, in the presence of alkylsulfonate and/or the alkyl sulfuric ester salt (emulsifying agent (e)) or in the presence of non-, will be by (methyl) acrylic acid alkyl ester compound (m2-1) 50～99.99 quality %, have 2 above carbon-to-carbon double bonds polymerizable unsaturated compound (m2-2) 0.01～5 quality % and can with other compounds (m2-3) 0～49.99 quality % of (methyl) acrylic acid alkyl ester compound (m2-1) and polymerizable unsaturated compound (m2-2) copolymerization (wherein, (m2-1), (m2-2) and (m2-3) add up to 100 quality %.) monomer (m2) that consists of carries out polymerization in aqueous medium, obtain the operation of multipolymer (a11).
And, with regard to the ratio that the monomer (m1) that uses in the above-mentioned polymerization process reaches usage quantity (m2), be made as in the total with both in the situation of 100 quality %, be respectively 1～50 quality % and 50～99 quality %.
Above-mentioned the 1st polymerization process be in the presence of emulsifying agent (e) will by (methyl) acrylic acid alkyl ester compound (m1-1) 50～100 quality % and can with other compounds (m1-2) 0～50 quality % of (methyl) acrylic acid alkyl ester compound (m1-1) copolymerization (wherein, (m1-1) and (m1-2) add up to 100 quality %.) monomer (m1) that consists of carries out letex polymerization in aqueous medium, form the operation of the 1st polymkeric substance.When polymerization, can use as required polymerization starter, chain-transfer agent (molecular weight regulator), ionogen etc.In addition, the applicable known method of the concrete grammar of letex polymerization.
As (methyl) acrylic acid alkyl ester compound (m1-1) of above-mentioned formation monomer (m1), the carbonatoms that preferably uses the alkyl of ester section is 1～14 compound, particularly preferably uses n-butyl acrylate and 2-EHA.In addition, above-mentioned (methyl) acrylic acid alkyl ester compound (m1-1) can be used separately, also can use more than 2 kinds.
In addition, as above-mentioned can with other compounds (m1-2) of (methyl) acrylic acid alkyl ester compound (m1-1) copolymerization, usually use the compound with 1 carbon-to-carbon double bond, preferably use aromatic ethenyl compound, vinyl cyanide based compound etc.In addition, these compounds may be used singly or in combination of two or more.
With regard to the ratio of (methyl) acrylic acid alkyl ester compound (m1-1) of using in above-mentioned the 1st polymerization process and other compounds (m1-2), be made as in the total with both in the situation of 100 quality %, be preferably respectively 50～100 quality % and 0～50 quality %, more preferably 70～100 quality % and 0～30 quality %, more preferably 90～100 quality % and 0～10 quality %.By being set as aforementioned proportion, the shock resistance of products formed and bright property are excellent, the generation of the wire drawing when the inhibition vibration is deposited.
In addition, in above-mentioned the 1st polymerization process, emulsifying agent (e) is existed, carry out the polymerization of monomer.By using mentioned emulsifier (e), can make efficiently that gel content is more than the 70 quality % be used to making, the swelling capacity of toluene is that 5.5～30 times, volume average particle size are that the ratio of 100～200nm and volume average particle size and number average bead diameter is less than the 1st polymkeric substance of 1.1 acrylic rubber matter polymkeric substance (a1).
As abovementioned alkyl sulfonate, can enumerate: sulfonated alkane, alkylbenzene sulfonate, sulfonated alkyl naphathalene etc.These compounds may be used singly or in combination of two or more.
Above-mentioned sulfonated alkane can use the compound of following general formula (1) expression.
R 1-SO 3M (1)
(in the formula, R 1Be the alkyl of carbonatoms 8～20, M is Na or K.)
The abovementioned alkyl benzene sulfonate can use the compound of following general formula (2) expression.
[changing 1]
Figure BDA00002478074600121
(in the formula, R 2Be the alkyl of carbonatoms 10～18, M is Na or K.)
In addition, the abovementioned alkyl naphthalenesulfonate can use the compound of following general formula (3) expression.
[changing 2]
Figure BDA00002478074600131
(in the formula, R 3Be the alkyl of carbonatoms 3～8, M is Na or K.)
As abovementioned alkyl sulfonate, preference chain alkyl sulfonate and alkylbenzene sulfonate, more preferably alkylbenzene sulfonate.As alkylbenzene sulfonate, Sodium dodecylbenzene sulfonate particularly preferably.
As the abovementioned alkyl sulfuric acid, can enumerate: higher alcohol sulfate salt, senior alkyl ether sulfuric acid, sulfated oil, sulfated fatty acid ester, sulfation alkene etc.These compounds may be used singly or in combination of two or more.
As the abovementioned alkyl sulfuric acid, can enumerate: sodium octyl sulfate, sodium 2-ethylhexyl sulfate, sodium decyl sulfate, Sodium Lauryl Sulphate BP/USP, lauryl potassium sulfate, Texapon Special, triethanolamine lauryl sulfate, Trombovar, stearyl sodium sulfate, Sodium palmityl sulfate, polyoxyethylene lauryl ether sodium sulfate etc.
In the situation that above-mentioned monomer (m1) is made as 100 mass parts, the usage quantity of mentioned emulsifier (e) is preferably 0.01～4.0 mass parts, more preferably 0.02～3.0 mass parts, more preferably 0.04～2.5 mass parts.The usage quantity of mentioned emulsifier (e) is when above-mentioned scope, can make efficiently be used to the 1st polymkeric substance of making the acrylic rubber matter polymkeric substance (a1) with above-mentioned character, in addition, can make the products formed that obtains become the products formed of shock resistance and bright property excellence.
In addition, and in the situation with above-mentioned alkylsulfonate and alkyl sulfuric ester salt, be made as in the total with both in the situation of 100 quality %, the ratio of its usage quantity is preferably respectively 1～99 quality % and 1～99 quality %, more preferably 5～95 quality % and 5～95 quality % are particularly preferably 10～90 quality % and 10～90 quality %.
Using method as the emulsifying agent (e) in above-mentioned the 1st polymerization process can be: the method for the reaction system of before polymerization total amount once being packed into; Before polymerization, a part is made an addition in the reaction system method of after polymerization begins, its remainder being separated or adding continuously; The method of after polymerization begins, separating or adding continuously etc.
In above-mentioned the 1st polymerization process, use in the situation of polymerization starter, can use organo-peroxide, azo based compound, inorganic peroxide, oxidation-reduction type polymerization starter etc.
As above-mentioned organo-peroxide, can enumerate: t-butyl hydroperoxide, tert-pentyl-tert-butyl peroxide, the tertiary butyl-uncle's hexyl superoxide, tert-pentyl-uncle's hexyl superoxide, two (uncle's hexyl) superoxide, Cyclohexanone peroxides, 3,3, the 5-trimethyl hexanone peroxide, methyl cyclohexanone peroxide, 1, two (t-butyl peroxy)-3 of 1-, 3, the 5-trimethyl-cyclohexane, 1, two (t-butyl peroxy) hexanaphthenes of 1-, normal-butyl-4, two (t-butyl peroxy) valerates of 4-, Cumene Hydroperoxide 80,2,5-dimethylhexane-2, the 5-dihydro-peroxidase, 1, two (the t-butyl peroxy)-sec.-propyl of 3-) benzene, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, the diisopropyl benzene superoxide, the tert-butyl peroxide cumyl, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, peroxidation 2, the 4-dichloro-benzoyl, the peroxidation lauric acid tert-butyl ester, the single carbonic acid tert-butyl ester of peroxidation, two (tert-butylcyclohexyl) peroxy dicarbonate, peroxidized t-butyl perbenzoate, 2,5-dimethyl-2,5-two (benzoyl peroxidation) hexane etc.
As above-mentioned azo based compound, can enumerate: 2,2 '-azo two (isopropyl cyanide), 1,1-azo two (hexanaphthene-1-nitrile), azocumenes, 2,2 '-azo two (2-methylbutyronitrile), 2, the two methyl pentane nitriles, 4 of 2 '-azo, 4 '-azo two (4-cyanopentanoic acid), 2-(tertiary butyl azo)-2-dicyanopropane, 2,2 '-azo two (2,4, the 4-trimethylpentane), 2,2 '-azo two (2-methylpropane), dimethyl 2,2 '-azo two (2 Methylpropionic acid ester) etc.
As above-mentioned inorganic peroxide, can enumerate: Potassium Persulphate, Sodium Persulfate, ammonium persulphate etc.
In addition, as the oxidation-reduction type polymerization starter, can use with S-WAT, Sulfothiorine, rongalite, xitix, ferrous sulfate etc. as reductive agent the oxidation-reduction type polymerization starter take potassium persulphate, hydrogen peroxide, t-butyl hydroperoxide etc. as oxygenant.
As above-mentioned polymerization starter, preferred inorganic peroxide.
In the situation that above-mentioned monomer (m1) is made as 100 mass parts, the usage quantity of above-mentioned polymerization starter is preferably 0.01～3.0 mass parts, 0.03～2.0 mass parts more preferably, more preferably 0.05～1.0 mass parts is particularly preferably 0.1～0.8 mass parts.The usage quantity of above-mentioned polymerization starter is when above-mentioned scope, can make efficiently be used to the 1st polymkeric substance of making the acrylic rubber matter polymkeric substance (a1) with above-mentioned character, in addition, can make the products formed that obtains become the products formed of shock resistance and bright property excellence.
Using method as the polymerization starter in above-mentioned the 1st polymerization process can be: the method for the reaction system of before polymerization total amount once being packed into; Before polymerization, a part is made an addition to reaction system, after polymerization begins with its remainder separately or the method for adding continuously etc.
In above-mentioned the 1st polymerization process, use in the situation of chain-transfer agent (molecular weight regulator), can use the halogenated hydrocarbons such as chloroform, carbon tetrabromide; The thio-alcohols such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, uncle's lauryl mercaptan, Thiovanic acid; The xanthan acids such as dimethyl yellow ortho acid disulphide, di-isopropyl xanthogenic acid disulphide; The present known compound such as terpinolene, α-methylstyrenedimer.In the above-mentioned chain-transfer agent, the preferred tertiary lauryl mercaptan.
In the situation that above-mentioned monomer (m1) is made as 100 mass parts, the usage quantity of above-mentioned chain-transfer agent is preferably below 3 mass parts, more preferably below 2 mass parts.When the usage quantity of above-mentioned chain-transfer agent was too much, the shock resistance of products formed became insufficient sometimes.
Using method as the chain-transfer agent in above-mentioned the 1st polymerization process can be: the method for the reaction system of before polymerization total amount once being packed into; Before polymerization, a part is made an addition to reaction system, after polymerization begins with its remainder separately or the method for adding continuously etc.
In above-mentioned the 1st polymerization process, use in the electrolytical situation, can use the present known compounds such as vitriolate of tartar, salt of wormwood, yellow soda ash, potassium hydroxide, sodium bicarbonate, trisodium phosphate, potassiumphosphate, V-Brite B.These compounds may be used singly or in combination of two or more.In the above-claimed cpd, preferred salt of wormwood, yellow soda ash, sodium bicarbonate and V-Brite B.
In the situation that above-mentioned monomer (m1) is made as 100 mass parts, above-mentioned electrolytical usage quantity is preferably 0.01～1.5 mass parts, more preferably 0.03～1.3 mass parts, more preferably 0.05～1.0 mass parts.Above-mentioned electrolytical usage quantity can be made the 1st polymkeric substance be used to the multipolymer (a11) that is made as the acrylic rubber matter polymkeric substance (a1) with above-mentioned character efficiently when above-mentioned scope.
Electrolytical using method as in above-mentioned the 1st polymerization process can be: the method for the reaction system of before polymerization total amount once being packed into; Before polymerization, a part is made an addition to reaction system, the method for after polymerization begins, its remainder being separated or adding continuously; The method of after polymerization begins, separating or adding continuously etc.
Polymerization temperature in above-mentioned the 1st polymerization process is generally 65 ℃～98 ℃, is preferably 70 ℃～95 ℃.In addition, polymerization time is generally 0.5～2.0 hour.
PH to the reaction system in above-mentioned the 1st polymerization process is not particularly limited, and is generally 2～12 scope.Maintain above-mentioned scope by the pH with reaction system, carry out simultaneously polymerization, can make efficiently the 1st polymkeric substance be used to the multipolymer (a11) that is made as the acrylic rubber matter polymkeric substance (a1) with above-mentioned character.
Above-mentioned the 1st polymerization process is preferred more than 85%, more preferably more than 90%, particularly preferably the moment more than 95% finishes at polymerisation conversion.In the situation that above-mentioned polymerisation conversion finishes when low, even sometimes use the 1st polymkeric substance that obtains to supply with the 2nd polymerization process, can not obtain having the acrylic rubber matter polymkeric substance (a1) of above-mentioned character.
In addition, in the situation that polymerisation conversion finishes above-mentioned the 1st polymerization process more than 85%, the volume average particle size of the 1st polymkeric substance that obtains is generally 40～120nm.
Above-mentioned the 2nd polymerization process is in the presence of above-mentioned the 1st polymkeric substance, in the presence of alkylsulfonate and/or the alkyl sulfuric ester salt (emulsifying agent (e)) or in the presence of non-, will be by (methyl) acrylic acid alkyl ester compound (m2-1) 50～99.99 quality %, have 2 above carbon-to-carbon double bonds polymerizable unsaturated compound (m2-2) 0.01～5 quality % and can with other compounds (m2-3) 0～49.99 quality % of (methyl) acrylic acid alkyl ester compound (m2-1) and polymerizable unsaturated compound (m2-2) copolymerization (wherein, (m2-1), (m2-2) and (m2-3) add up to 100 quality %.) monomer (m2) that consists of carries out polymerization in aqueous medium, obtain the operation of multipolymer.
Above-mentioned the 2nd polymerization process can carry out in the reaction system identical with the 1st polymerization process, also can carry out in different reaction systems.In the situation of in different reaction systems, carrying out, can in the presence of emulsifying agent (e), carry out polymerization, also can in the presence of emulsifying agent (e) non-, carry out.In the latter's the situation, can use other emulsifying agents.
In the situation that use emulsifying agent in above-mentioned the 2nd polymerization process, can use as required polymerization starter, chain-transfer agent (molecular weight regulator), ionogen etc.As these compositions, all can use above-mentioned illustrative compound.
As (methyl) acrylic acid alkyl ester compound (m2-1) that consists of above-mentioned monomer (m2), the carbonatoms that preferably uses the alkyl of ester section is 1～14 compound, particularly preferably uses n-butyl acrylate and 2-EHA.In addition, above-mentioned (methyl) acrylic acid alkyl ester compound (m2-1) can be used separately, also can use more than 2 kinds.
As above-mentioned polymerizable unsaturated compound (m2-2) with 2 above carbon-to-carbon double bonds, preferred (methyl) acrylate that use 2 functionality aromatic ethenyl compounds, 2 functionalities (methyl) acrylate, 3 functionalities (methyl) acrylate, 4 functionalities (methyl) acrylate, 5 functionalities (methyl) acrylate, 6 functionalities (methyl) acrylate, polyvalent alcohol etc. particularly preferably use allyl methacrylate(AMA) and triallyl cyanurate.In addition, above-mentioned polymerizable unsaturated compound (m2-2) can use separately, also can use more than 2 kinds.
In addition, as can with other compounds (m2-3) of above-mentioned (methyl) acrylic acid alkyl ester compound (m2-1) and above-mentioned polymerizable unsaturated compound (m2-2) copolymerization, usually use the compound with 1 carbon-to-carbon double bond, preferably use aromatic ethenyl compound, vinyl cyanide based compound etc.In addition, these compounds may be used singly or in combination of two or more.
With regard to regard to the ratio of (methyl) acrylic acid alkyl ester compound (m2-1) of using in above-mentioned the 2nd polymerization process, polymerizable unsaturated compound (m2-2) and other compounds (m2-3), be made as in the total with them in the situation of 100 quality %, be preferably respectively 50～99.99 quality %, 0.01～5.0 quality % and 0～49.99 quality %, more preferably 70～99.99 quality %, 0.01～3.0 quality % and 0～29.99 quality %, more preferably 90～99.99 quality %, 0.01～2.0 quality % and 0～9.99 quality %.By being set as aforementioned proportion, the shock resistance of products formed and bright property are excellent, the generation of the wire drawing when the inhibition vibration is deposited.
In addition, with regard to the ratio of the usage quantity of the monomer (m2) that uses in the monomer (m1) that uses in above-mentioned the 1st polymerization process and above-mentioned the 2nd polymerization process, be set as in the total with both in the situation of 100 quality %, be preferably respectively 1～50 quality % and 50～99 quality %, more preferably 3～40 quality % and 60～97 quality % are particularly preferably 5～35 quality % and 65～95 quality %.By being set as aforementioned proportion, the shock resistance of products formed and bright property are excellent, the generation of the wire drawing when the inhibition vibration is deposited.
Above-mentioned the 2nd polymerization process in the presence of the 1st polymkeric substance that in above-mentioned the 1st polymerization process, obtains with the operation of above-mentioned monomer (m2) polymerization, the total amount of monomer (m2) once can be made an addition to reaction system and carries out polymerization, also can separate on one side or add continuously monomer (m2), Yi Bian carry out polymerization.About the using method of emulsifying agent, polymerization starter, chain-transfer agent (molecular weight regulator) etc., can with above-mentioned the 1st polymerization process in method same.
As mentioned above, above-mentioned the 2nd polymerization process can carry out in the reaction system identical with the 1st polymerization process, also can carry out in different reaction systems.
In the reaction system identical with the 1st polymerization process, carry out in the situation of above-mentioned the 2nd polymerization process, add above-mentioned monomer (m2) in the latex that contains the 1st polymkeric substance that in the 1st polymerization process, obtains and carry out polymerization getting final product, also can again add as required aqueous medium etc.
In addition, in new reaction system, carry out can be used as it is the latex that contains the 1st polymkeric substance that obtains in above-mentioned the 1st polymerization process in the situation of above-mentioned the 2nd polymerization process, also can use as required the suspension that this latex is suspended.
Carry out in the situation of above-mentioned the 2nd polymerization process in the presence of mentioned emulsifier (e), the using method of the preferred combination of the preferred kind of emulsifying agent (e), alkylsulfonate and alkyl sulfuric ester salt and emulsifying agent (e) and in above-mentioned the 1st polymerization process those are same.
In addition, in the situation that above-mentioned monomer (m2) is made as 100 mass parts, the usage quantity of mentioned emulsifier (e) is preferably 0.01～4.0 mass parts, more preferably 0.02～3.0 mass parts, more preferably 0.04～2.5 mass parts.The usage quantity of mentioned emulsifier (e) is when above-mentioned scope, can make efficiently as the multipolymer (a11) with acrylic rubber matter polymkeric substance (a1) of above-mentioned character, in addition, the products formed that obtains can be made the products formed of shock resistance and bright property excellence.
And, in the situation that use polymerization starter, chain-transfer agent (molecular weight regulator), ionogen etc. in above-mentioned the 2nd polymerization process, compound and using method that preferred use is identical with the situation of using these materials in above-mentioned the 1st polymerization process.About the usage quantity of each composition, monomer (m1) can be replaced by monomer (m2), use identical amount.
Polymerization temperature in above-mentioned the 2nd polymerization process is generally 65 ℃～98 ℃, is preferably 70 ℃～95 ℃.In addition, polymerization time is generally 2.0～8.0 hours.
PH to the reaction system in above-mentioned the 2nd polymerization process is not particularly limited, and is generally 2～12 scope.Carry out polymerization on one side by on one side the pH of reaction system being maintained above-mentioned scope, can make efficiently as the multipolymer (a11) with acrylic rubber matter polymkeric substance (a1) of above-mentioned character.
Above-mentioned the 2nd polymerization process is preferred more than 85%, more preferably more than 90%, particularly preferably the moment more than 95% finishes at polymerisation conversion.In the situation that polymerisation conversion finishes above-mentioned the 2nd polymerization process more than 85%, can make efficiently as the multipolymer (a11) with acrylic rubber matter polymkeric substance (a1) of above-mentioned character.In addition, reduce above-mentioned polymerisation conversion and when finishing polymerization, the particle diameter of the acrylic rubber matter polymkeric substance that sometimes obtains is little, it is insufficient that shock resistance becomes.
Acid is rubber polymer (a1) as aforesaid propylene, headed by the multipolymer that can use to obtain as described above (a11), makes and utilizes at present the acrylic rubber matter polymkeric substance hypertrophyization that known method obtains and the polymkeric substance that obtains.
As the method for hypertrophy processing, can be set forth in the method that contains acid such as adding acetic anhydride, acetic acid, nitric acid, phosphoric acid in the latex of hypertrophyization with polymkeric substance.Wherein, preferred acetic anhydride, thus, the particle diameter that can make behind hypertrophy does not have acrylic rubber matter polymkeric substance devious (a1).
Acid is rubber polymer (a1) as aforesaid propylene, can use any of polymkeric substance of the polymkeric substance that do not have hypertrophyization and hypertrophyization, also they can be used in combination.
Aforesaid propylene acid be rubber polymer (a1) in the presence of in the ethene base system monomer (a2) of polymerization for containing the monomer of aromatic ethenyl compound and vinyl cyanide based compound, can contain as required (methyl) acrylic compound, maleimide amine compound, unsaturated acid anhydride, contain carboxyl unsaturated compound, hydroxyl unsaturated compound, contain amino unsaturated compound, contain the amido unsaturated compound, contain the epoxy group(ing) unsaturated compound, contain
Figure BDA00002478074600191
Azoles quinoline base unsaturated compound etc.In addition, the ratio of the aromatic ethenyl compound in the above-mentioned ethene base system monomer (a2) and the total amount of vinyl cyanide based compound is preferably 50～100 quality %, more preferably 70～100 quality %, more preferably 80～100 quality %.
Above-mentioned aromatic ethenyl compound is not particularly limited, for not having the substituent compounds such as functional group.As the example, can enumerate: vinylbenzene, alpha-methyl styrene, o-methyl styrene, p-methylstyrene, Beta-methyl vinylbenzene, ethyl styrene, p-tert-butylstyrene, Vinyl toluene, vinyl-dimethyl benzene, vinyl naphthalene etc.These compounds can be used singly or in combination more than 2 kinds.In addition, wherein optimization styrene and alpha-methyl styrene, particularly preferably vinylbenzene.
As above-mentioned vinyl cyanide based compound, can enumerate: vinyl cyanide, methacrylonitrile, ethyl acrylonitrile, α-ethyl acrylonitrile, α-sec.-propyl vinyl cyanide etc.These compounds can be used singly or in combination more than 2 kinds.In addition, preferred vinyl cyanide wherein.
As above-mentioned (methyl) acrylic compound, can enumerate: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) Ethyl acrylate, (methyl) vinylformic acid n-octyl, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate etc.These compounds can be used singly or in combination more than 2 kinds.
As above-mentioned maleimide amine compound, can enumerate: maleimide, N-methyl maleimide, N-sec.-propyl maleimide, the N-butyl maleimide, N-dodecyl maleimide, N-phenylmaleimide, N-(2-aminomethyl phenyl) maleimide, N-(4-aminomethyl phenyl) maleimide, N-(2, the 6-3,5-dimethylphenyl) maleimide, N-(2,6-diethyl phenyl) maleimide, N-(2-p-methoxy-phenyl) maleimide, N-benzyl maleimide, N-naphthyl maleimide, N-N-cyclohexylmaleimide etc.Wherein, preferred N-phenylmaleimide.In addition, these compounds can be used singly or in combination more than 2 kinds.In addition, as the additive method that in mentioned component [A], imports from the structural unit of maleimide amine compound, can for for example the unsaturated dicarboxylic acid acid anhydride of maleic anhydride being carried out copolymerization, carry out thereafter the method for imidization.
As above-mentioned unsaturated acid anhydride, can enumerate: maleic anhydride, itaconic anhydride, citraconic anhydride etc.These compounds can be used singly or in combination more than 2 kinds.
As the above-mentioned carboxyl unsaturated compound that contains, can enumerate: (methyl) vinylformic acid, ethylacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid, β-crotonic acid, styracin etc.These compounds can be used singly or in combination more than 2 kinds.
As above-mentioned hydroxyl unsaturated compound, can enumerate: (methyl) vinylformic acid hydroxy methyl, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 3-hydroxyl butyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, the compound that makes (methyl) vinylformic acid 2-hydroxy methacrylate addition 6-caprolactone and obtain etc. has (methyl) acrylate of hydroxyl; O-hydroxy ethene, between hydroxy styrenes, 4-Vinyl phenol, adjacent hydroxyl-alpha-vinyl toluene, between hydroxyl-alpha-vinyl toluene, to hydroxyl-alpha-vinyl toluene, 2-hydroxymethyl-alpha-methyl styrene, 3-hydroxymethyl-alpha-methyl styrene, 4-hydroxymethyl-alpha-methyl styrene, 4-hydroxymethyl-1-vinyl naphthalene, 7-hydroxymethyl-1-vinyl naphthalene, 8-hydroxymethyl-1-vinyl naphthalene, 4-hydroxymethyl-1-pseudoallyl naphthalene, 7-hydroxymethyl-1-pseudoallyl naphthalene, 8-hydroxymethyl-1-pseudoallyl naphthalene, N-(4-hydroxy phenyl) maleimide, to vinyl benzyl alcohol, 3-hydroxyl-1-propylene, the 4-hydroxyl-1-butene, cis-4-hydroxyl-2-butylene, trans-4-hydroxyl-2-butylene, 3-hydroxy-2-methyl-1-propylene etc.These compounds can be used singly or in combination more than 2 kinds.
Contain amino unsaturated compound as above-mentioned, can enumerate: (methyl) acrylic-amino ethyl ester; (methyl) vinylformic acid propyl group amino ethyl ester; (methyl) vinylformic acid dimethylamino methyl esters; (methyl) vinylformic acid diethylamino methyl esters; (methyl) vinylformic acid 2-dimethylamino ethyl ester; (methyl) vinylformic acid 2-diethylamino ethyl ester; (methyl) vinylformic acid 2-(two-n-propyl is amino) ethyl ester; (methyl) vinylformic acid 2-dimethylamino propyl ester; (methyl) vinylformic acid 2-diethylamino propyl ester; (methyl) vinylformic acid 2-(two-n-propyl is amino) propyl ester; (methyl) vinylformic acid 3-dimethylamino propyl ester; (methyl) vinylformic acid 3-diethylamino propyl ester; (methyl) vinylformic acid 3-(two-n-propyl is amino) propyl ester; (methyl) vinylformic acid 2-tertiary butyl amino ethyl ester; (methyl) vinylformic acid phenyl amino ethyl ester; (methyl) acrylic-amino ether; 4-amino-benzene ethene; 4-dimethylamino vinylbenzene; N-vinyl diethylamide; N-ethanoyl vinyl amine; (methyl) acrylamide; N-methyl (methyl) acrylamide etc.These compounds can be used singly or in combination more than 2 kinds.
As the above-mentioned amido unsaturated compound that contains, can enumerate: (methyl) acrylamide, N-methylol (methyl) acrylamide, 3-dimethylaminopropyl (methyl) acrylamide etc.These compounds can be used singly or in combination more than 2 kinds.
As the above-mentioned epoxy group(ing) unsaturated compound that contains, can enumerate: (methyl) glycidyl acrylate, (methyl) vinylformic acid 3,4-oxygen cyclohexyl, vinyl glycidyl ether, glycidyl allyl ether, methacrylic glycidyl ether etc.These compounds can be used singly or in combination more than 2 kinds.
Contain as above-mentioned
Figure BDA00002478074600211
Azoles quinoline base unsaturated compound can be enumerated vinyl
Figure BDA00002478074600212
Azoles quinoline etc.
As mentioned component [A], preferred graft resin is as described below.
(1) in the presence of acrylic rubber matter polymkeric substance (a1), will carry out polymerization by the ethene base system monomer (a2-1) that aromatic ethenyl compound and vinyl cyanide based compound consist of and the resin that obtains;
(2) in the presence of acrylic rubber matter polymkeric substance (a1), will carry out polymerization by the ethene base system monomer (a2-2) that aromatic ethenyl compound, vinyl cyanide based compound and (methyl) acrylic compound consist of and the resin that obtains.
As mentioned above, mentioned component [A] is by acrylic rubber matter polymkeric substance section and the multipolymer section formation that contains from the structural unit of ethene base system monomer (a2).From the shock resistance of products formed and the viewpoint of bright property, total 100 mass parts with respect to acrylic rubber matter polymkeric substance section and multipolymer section, the content that consists of the acrylic rubber matter polymkeric substance section of this composition [A] is preferably 5～80 mass parts, more preferably 10～70 mass parts, more preferably 10～65 mass parts.In addition, aforesaid propylene acid is the content of rubber polymer section when too much, and the productivity of acrylic rubber matter enhancing by polymer graft resin, thermotolerance and bright property reduce sometimes.On the other hand, when the content of acrylic rubber matter polymkeric substance section was very few, shock resistance was insufficient sometimes.
The method of making mentioned component [A] is not particularly limited, and can be suitable for known method.As the method for graft polymerization, can be for letex polymerization, suspension polymerization, solution polymerization, mass polymerization or with the polymerization of these Combination of Methods.Wherein, preferred emulsion polymerization.In addition, in above-mentioned polymerization, except composition [A], by-product is graftomer not.
Make in the situation of mentioned component [A], the usage quantity of acrylic rubber matter polymkeric substance (a1) and ethene base system monomer (a2), viewpoint from shock resistance and bright property, be made as in the total amount with both in the situation of 100 quality %, be preferably respectively 5～90 quality % and 10～95 quality %, more preferably 10～80 quality % and 20～90 quality %, more preferably 30～70 quality % and 30～70 quality %.
In addition, when making mentioned component [A], can in reaction system, add ethene base system monomer (a2) next time and begin polymerization in the existence of acrylic rubber matter polymkeric substance (a1) total amount, while also can separate or add continuously and carry out polymerization.In addition, can be in the presence of the part of acrylic rubber matter polymkeric substance (a1) or non-existence add ethene base system monomer (a2) next time and begin polymerization, also can separate or add continuously.At this moment, can reaction midway once, separately or add continuously the remainder that aforesaid propylene acid is rubber polymer (a1).
In the situation that carry out letex polymerization, can use polymerization starter, chain-transfer agent (molecular weight regulator), emulsifying agent, water etc.About polymerization starter and chain-transfer agent, as described above.
As above-mentioned polymerization starter, preferential oxidation reduced form polymerization starter.In addition, with respect to above-mentioned ethene base system monomer (a2) total amount, the usage quantity of above-mentioned polymerization starter is generally 0.1～1.5 quality %.
In addition, above-mentioned polymerization starter can once or continuously make an addition in the reaction system.
As above-mentioned chain-transfer agent, preferred thio-alcohol, particularly preferably uncle's lauryl mercaptan.In addition, with respect to above-mentioned ethene base system monomer (a2) total amount, the usage quantity of above-mentioned chain-transfer agent is generally below the 5 quality %.
In addition, above-mentioned chain-transfer agent can once or continuously make an addition in the reaction system.
As mentioned emulsifier, can enumerate negatively charged ion is that tensio-active agent and nonionic are tensio-active agent.Be tensio-active agent as negatively charged ion, can enumerate: the sulfuric ester of higher alcohols; The alkylbenzene sulfonates such as Sodium dodecylbenzene sulfonate; The aliphatic sulfonates such as Sodium Lauryl Sulphate BP/USP; Senior aliphatic carboxylate, aliphatics phosphoric acid salt etc.In addition, be tensio-active agent as nonionic, can enumerate: the alkyl ester type compound of polyoxyethylene glycol, alkyl ether type compound etc.These materials can use separately a kind or be used in combination more than 2 kinds.With respect to above-mentioned ethene base system monomer (a2) total amount, the usage quantity of mentioned emulsifier is generally 0.01～5 quality %.
Letex polymerization can according to kind and the cooperation of ethene base system monomer (a2), polymerization starter etc., be carried out under known condition.
Polymerization temperature when above-mentioned ethene base system monomer (a2) is carried out polymerization is generally 40 ℃～80 ℃, is preferably 50 ℃～75 ℃.In addition, polymerization time is generally 4～8 hours.
The pH of the reaction system in the letex polymerization is not particularly limited, and is generally 8～12 scope, is preferably 9～12.Carry out polymerization on one side by on one side the pH of reaction system being maintained above-mentioned scope, can carry out efficiently the formation of composition [A].
Letex polymerization is preferred more than 85%, more preferably more than 90%, particularly preferably the moment more than 95% finishes at polymerisation conversion.In the situation that polymerisation conversion finishes this letex polymerization more than 85%, can use the composition that contains the composition [A] that obtains to obtain the products formed of shock resistance and bright property excellence.
After letex polymerization finishes, the latex that contains composition [A] is utilized usually the solidifying of resinous principle of peptizer, make powder etc.Thereafter, wait by washing make with extra care, dry and reclaim.When solidifying, can use present known peptizer, can use the inorganic salt such as calcium chloride, sal epsom, magnesium chloride, calcium acetate; The mineral acid such as sulfuric acid, hydrochloric acid; The organic acid such as acetic acid, lactic acid etc.
Make by solution polymerization, mass polymerization and body-suspension polymerization in the situation of composition [A], can be suitable for known method.
Because containing composition [A] usually, the rubber reinforced resin that obtains as described above reaches not graftomer, therefore, composition [A] is reached in the situation that graftomer does not separate, applicable following method: for example, the rubber reinforced resin of 1g is dropped in the acetone of 20～30ml, under 25 ℃, carry out 2～6 hours stirring etc., insoluble minute of generating and solvable minute (acetone soluble polymer) are separated, reclaimed.
The acetone soluble polymer is equivalent to not graftomer, as mentioned above, according to the kind of the ethene base system monomer (a2) that uses, has the material that is included in composition [C] and/or the composition [D].
Viewpoint from forming process, shock resistance, bright property etc., percentage of grafting in the mentioned component [A], namely the ratio that contains from the multipolymer of the structural unit of ethene base system monomer (a2) in the upper grafting of acrylic rubber matter polymkeric substance (a1) is preferably 5～200 quality %, more preferably 10～150 quality %, more preferably 20～120 quality %.Percentage of grafting is crossed when hanging down, and the shock resistance of products formed is insufficient sometimes.On the other hand, when percentage of grafting was too high, forming process was insufficient sometimes.
Above-mentioned percentage of grafting can utilize following formula to obtain.
Percentage of grafting (%)=(S-T)/T} * 100
In the formula, S will be for dropping into by the rubber reinforced resin that graft polymerization obtains in the acetone, after using bobbing machine vibration (temperature 23 ℃, 2 hours), use separating centrifuge to carry out centrifugation (0 ℃ of temperature, revolution 28,000rpm, 1 hour), with the quality (g) of insoluble minute and insoluble minute (temperature 60 C, 12 hours dryings) being isolated in solvable minute, T is the quality (g) of acrylic rubber matter polymkeric substance (a1) contained in the rubber reinforced resin.The quality of this acrylic rubber matter polymkeric substance (a1) can be by being calculated by polymerization formula and polymerisation conversion method, utilize method that infrared absorption spectrum (IR) obtains etc. to obtain.
Above-mentioned percentage of grafting can be adjusted by suitably selecting such as the supply method of the kind of the kind of the polymerization starter that uses when the manufacturing of composition [A] and usage quantity thereof, chain-transfer agent and usage quantity thereof, ethene base system monomer (a2) and service time, polymerization temperature etc.
Mentioned component [B] for contain organo-siloxane be rubber and have from the compounded rubber (b1) of (be total to) polymer rubber of the structural unit of (methyl) alkyl acrylate in the presence of, will contain (methyl) acrylic acid alkyl ester compound, aromatic ethenyl compound and the vinyl cyanide based compound of second-order transition temperature above 0 ℃ of homopolymer ethene base system monomer (below be also referred to as " ethene base system monomer (b2) ".) carry out polymerization (graft polymerization) and the compounded rubber that obtains strengthens graft resin.
Mentioned component [B] and mentioned component [A] are similarly, the multipolymer of ethene base system monomer (b2) is the resin in the upper grafting of compounded rubber (b1), for by compounded rubber section with contain the resin that the multipolymer section from the structural unit of ethene base system monomer (b2) consists of.
The compounded rubber (b1) that is used for the formation of mentioned component [B] is to be that rubber and (be total to) polymer rubber of having from the structural unit of (methyl) alkyl acrylate consist of by organo-siloxane, is that both such as pass through to twine mutually at the mutual not rubber of Composite independently.Be rubber as organo-siloxane, preferred organopolysiloxane described later (b1-1), as (being total to) polymer rubber that contains from the structural unit of (methyl) alkyl acrylate, poly-(methyl) acrylate (b1-2) preferred described later.
As the compounded rubber (b1) that contains above-mentioned organopolysiloxane (b1-1) and poly-(methyl) acrylate (b1-2), can use and utilize in the presence of organopolysiloxane (b1-1), will contain the monomer of (methyl) acrylic acid alkyl ester compound (hereinafter referred to as " monomer (mm) ".) carry out the rubber that the method for polymerization obtains; Or utilize in the presence of poly-(methyl) acrylate (b1-2), organo-siloxane is carried out the rubber that the method for polymerization obtains.Wherein, from the viewpoint of shock resistance, bright property and the productivity of products formed, preferably utilize the compounded rubber of the former method, below, the method is described in detail.
As above-mentioned organopolysiloxane (b1-1), the material that preferred cyclic organic siloxane links via grafting intersection agent preferably will contain 3 yuan of rings above cyclic organic siloxane and organopolysiloxane and intersect agent (hereinafter referred to as " agent of siloxanes intersection " with grafting.) the organo-siloxane mixture carry out letex polymerization and the material that obtains.The organo-siloxane mixture can contain organopolysiloxane as required uses linking agent (hereinafter referred to as " siloxane crosslinker ".)。
As above-mentioned 3 yuan of cyclic organic siloxanes more than the ring, the compound of preferred 3～6 yuan of rings.As cyclic organic siloxane, can enumerate: hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane, ten diformazan basic rings, six siloxanes, trimethyl triphenyl cyclotrisiloxane, tetramethyl tetraphenyl cyclotetrasiloxane, octaphenylcyclotetrasiloxane etc.These materials may be used singly or in combination of two or more.
Intersect agent as above-mentioned siloxanes, preferably with above-mentioned cyclic organic siloxane via siloxane bond bonding, can form with poly-(methyl) acrylate (b1-2), ethene base system monomer described later (b2) material of key.From with reactive viewpoint of above-mentioned cyclic organic siloxane, preferably have the alkoxysilane compound containing trialkylsilyl group in molecular structure of vinyl.
As above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure, can enumerate: Beta-methyl acryloxy ethyl dimethoxy-methyl silane, γ-methacryloxypropyl dimethoxy-methyl silane, γ-methacryloxypropyl methoxyl group dimethylsilane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl oxyethyl group diethylsilane, γ-methacryloxypropyl diethoxymethyl silane, the δ-methacryloxypropyl silanes such as methacryloxy butyl diethoxymethyl silane; The vinylsiloxanes such as tetramethyl-tetrem thiazolinyl cyclotetrasiloxane; To vinyl benzene base silanes such as ethenylphenyl dimethoxy-methyl silane; The hydrosulphonyl silanes such as γ-sulfydryl propyl group dimethoxy-methyl silane, γ mercaptopropyitrimethoxy silane.These compounds may be used singly or in combination of two or more.
As above-mentioned siloxane crosslinker, preferably has the compound of 3 or 4 energy and the functional group of above-mentioned cyclic organic siloxane bonding.As such compound, can enumerate: the tri-alkoxy alkyl silanes such as trimethoxymethylsila,e; The tri-alkoxy aryl-silanes such as triethoxyphenylsilan; The tetraalkoxysilanes such as tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, four butoxy silanes etc.These materials may be used singly or in combination of two or more.In addition, wherein preferred tetraalkoxysilane, particularly preferably tetraethoxysilane.
Above-mentioned organo-siloxane mixture is intersected by cyclic organic siloxane, siloxanes in the situation that agent and siloxane crosslinker consist of, the ratio of the usage quantity of these compositions, be made as in the total with them in the situation of 100 quality %, be preferably respectively 60～99.9 quality %, 0.1～10 quality % and 0～30 quality %.In addition, the particularly preferred usage quantity of above-mentioned cyclic organic siloxane is 70～99.9 quality %.
The letex polymerization of above-mentioned organo-siloxane mixture can be enumerated following method.
(1) in the organo-siloxane mixture, adds emulsifying agent and water and obtain latex, behind the corpusculed that carries out latex, itself and acid catalyst are mixed and make the method for its reaction.
(2) in the organo-siloxane mixture, add acid catalyst and make latex with emulsifying agent and water, carry out the corpusculed of latex and make the method for its reaction.
As mentioned emulsifier, can enumerate: the negatively charged ion such as sodium alkyl benzene sulfonate, alkyl sodium sulfonate, polyxyethylated sodium sulfate are emulsifying agent etc.These compounds may be used singly or in combination of two or more.In addition, the emulsifying agent of the sulfonate such as preferred alkyl benzene sulfonic acid sodium salt, alkyl sodium sulfonate system wherein.
In order to keep the stable dispersion state of latex, with respect to organo-siloxane mixture 100 mass parts, the usage quantity of mentioned emulsifier is preferably more than 0.05 mass parts.In addition, painted, the thermoplastic resin composition's who himself causes for fear of emulsifying agent the deteriorated painted impact that causes, higher limit is preferably 15 mass parts.
As above-mentioned acid catalyst, can enumerate: the sulphonic acids such as alkylsulphonic acid, alkyl benzene sulphonate (ABS), alkyl naphthalene sulfonic acid; The inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid.These materials may be used singly or in combination of two or more.In addition, wherein, consider preferred alkyl Phenylsulfonic acid, more preferably dodecyl Phenylsulfonic acid from the static stabilization of the latex that contains organopolysiloxane is excellent.
With respect to organo-siloxane mixture 100 mass parts, the usage quantity of above-mentioned acid catalyst is preferably 0.1～15 mass parts.
As the using method of the acid catalyst in the aforesaid method (1), the preferred acid catalyst aqueous solution that is dissolved in water and forms that uses.Preferably the acid catalyst aqueous solution is become after the high temperature by heating, in this aqueous solution, drip the latex of corpusculed with certain speed, carry out polyreaction.The method (1) is easily controlled the particle diameter of the organopolysiloxane that obtains, and is preferred.
In addition, in aforesaid method (2), acid catalyst can be directly used, also the acid catalyst aqueous solution that is dissolved in water and forms can be used.And, can make an addition to acid catalyst or the acid catalyst aqueous solution in organo-siloxane mixture, emulsifying agent and the water and mix.
When the letex polymerization of above-mentioned organo-siloxane mixture, as the device that latex is carried out corpusculed, can enumerate the shearing force that the lyophobic dust in the latex is formed with high speed rotating and make atomic homogeneous mixer, make atomic homogenizer etc. with the ejection power of high pressure generator formation.Wherein, the high pressure emulsifier units such as homogenizer can obtain the little latex of particle diameter distribution width of organo-siloxane mixture, and are therefore preferred.
The polymerization time relevant with the formation of above-mentioned organopolysiloxane (b1-1), in aforesaid method (1), the dropping of latex finishes rear preferred about 1 hour.On the other hand, in aforesaid method (2), polymerization time was preferably more than 2 hours, more preferably more than 5 hours.
In addition, polymerization temperature all is being preferably in any situation more than 50 ℃, more preferably more than 80 ℃.
Stopping of letex polymerization can be by with reaction solution cooling, further with in the alkaline matters such as sodium hydroxide, potassium hydroxide, yellow soda ash and carry out.
The volume average particle size of the organopolysiloxane (b1-1) that obtains by above operation is preferably below the 120nm, more preferably below the 100nm.Wherein, lower limit is generally 60nm.
Thereafter, carry out polymerization by the monomer (mm) that in the presence of the organopolysiloxane that obtains (b1-1), will contain (methyl) acrylic acid alkyl ester compound, can access the compounded rubber (b1) that contains organopolysiloxane (b1-1) and poly-(methyl) acrylate (b1-2).
Above-mentioned monomer (mm) can only be (methyl) acrylic acid alkyl ester compound, also can be made of (methyl) acrylic acid alkyl ester compound and other compounds.
The carbonatoms that above-mentioned (methyl) acrylic acid alkyl ester compound is preferably the alkyl of ester section is 1～14 compound.Its concrete example is: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) 2-EHA, (methyl) Octyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) tridecyl acrylate etc.These compounds can use separately, also can use more than 2 kinds.
As above-mentioned (methyl) acrylic acid alkyl ester compound, preferred methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, n-butyl acrylate, N-Hexyl methacrylate, (methyl) 2-EHA, lauryl methacrylate and methacrylic acid tridecyl ester, particularly preferably n-butyl acrylate and 2-EHA.
As other compounds, so long as can with the compound of (methyl) acrylic acid alkyl ester compound copolymerization, just be not particularly limited, except (methyl) acrylic acid alkyl ester compound, can enumerate the compound with 1 carbon-to-carbon double bond, the compound with 2 above carbon-to-carbon double bonds etc.
As other compounds, preferably have the compound of 2 above carbon-to-carbon double bonds, poly-(methyl) acrylate of preferred use intersects agent (hereinafter referred to as " agent of acrylic acid series intersection " with grafting.) and gather (methyl) acrylate and use linking agent (hereinafter referred to as " acrylic acid series linking agent ".)。
Aforesaid propylene acid system intersects agent and is preferably in a plurality of carbon-to-carbon double bonds contained in the molecule reactive different compound from (methyl) acrylic compound.
As the intersection agent of aforesaid propylene acid system, can enumerate: (methyl) allyl acrylate, triallyl cyanurate, triallyl isocyanurate etc.These materials may be used singly or in combination of two or more.
Aforesaid propylene acid is that linking agent is preferably the compound that forms crosslinking structure in poly-(methyl) acrylate (b1-2).
Acid is linking agent as aforesaid propylene, can enumerate: ethylene glycol bisthioglycolate (methyl) acrylate, glycol ether two (methyl) acrylate, triglycol two (methyl) acrylate, Tetraglycol 99 two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, butyleneglycol two (methyl) acrylate, hexylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetra methylol four (methyl) acrylate, Vinylstyrene.These materials may be used singly or in combination of two or more.
Above-mentioned monomer (mm) can be made of (methyl) acrylic acid alkyl ester compound and the agent of acrylic acid series intersection, also can be made of (methyl) acrylic acid alkyl ester compound, acrylic acid series intersection agent and acrylic acid series linking agent.
The usage rate of above-mentioned (methyl) acrylic acid alkyl ester compound, acrylic acid series intersection agent and acrylic acid series linking agent, be made as in the total with them in the situation of 100 quality %, be preferably respectively 80～99.99 quality %, 0.01～10 quality % and 0～10 quality %.In addition, the particularly preferred usage quantity of (methyl) acrylic acid alkyl ester compound is 90～99.99 quality %.
If the usage quantity of the intersection of the acrylic acid series in the above-mentioned monomer (mm) agent is more than the 0.01 quality %, then poly-(methyl) acrylate (b1-2) becomes the material with sufficient graft polymerization starting point, if it is below the 10 quality %, then can keep the caoutchouc elasticity of poly-(methyl) acrylate (b1-2).
In addition, if the usage quantity of the acrylic acid series linking agent in the above-mentioned monomer (mm) is below the 10 quality %, then can keep the caoutchouc elasticity of poly-(methyl) acrylate (b1-2).
In the situation that above-mentioned organopolysiloxane (b1-1) is made as 100 mass parts, confession is preferably 400～9 in the usage quantity of the monomer (mm) of polymerization in the presence of above-mentioned organopolysiloxane (b1-1), 900 mass parts, more preferably 900～1,900 mass parts.The usage quantity of above-mentioned monomer (mm) can obtain giving the compounded rubber (b1) of the products formed of shock resistance and bright property excellence efficiently when above-mentioned scope.
Stating in the use organopolysiloxane (b1-1) and monomer (mm) makes in the situation of compounded rubber (b1), can enumerate such as after in the latex that contains organopolysiloxane (b1-1), adding as required water, polymerization starter, emulsifying agent, chain-transfer agent (molecular weight regulator) etc., while supply with the method that monomer (mm) carries out polymerization.At this moment, the supply of monomer (mm) can once or separately be carried out, and can carry out continuously.
At this moment, the monomer of supplying with (mm) can directly use, and maybe can adopt the emulsification that uses in advance the mixture preparation that contains monomer (mm), emulsifying agent and water.In the latter's the situation, can use the emulsification that monomer (mm) is carried out corpusculed and form.
As above-mentioned polymerization starter, can enumerate: organo-peroxide, azo based compound, inorganic peroxide, oxidation-reduction type polymerization starter etc.Wherein, preferential oxidation reduced form polymerization starter, the combination of the particularly preferably combination of ferrous sulfate trisodium phosphate glucose hydrogen peroxide, ferrous sulfate Calcium Disodium Versenate salt rongalite hydrogen peroxide etc.
In the situation that above-mentioned monomer (mm) is made as 100 mass parts, the usage quantity of above-mentioned polymerization starter is preferably 0.01～5 mass parts, more preferably 0.05～3 mass parts.The usage quantity of above-mentioned polymerization starter can be made compounded rubber (b1) efficiently when above-mentioned scope, in addition, the products formed that obtains can be made the products formed of shock resistance and bright property excellence.
As mentioned emulsifier, can enumerate: the carboxylate salts such as sodium sarcosinate, lipid acid potassium, sodium soap, alkenyl succinic dipotassium, RA rosin acid; Alkyl sulfuric ester; Sodium alkyl benzene sulfonate; Alkyl sodium sulfonate; The negatively charged ion such as polyxyethylated sodium sulfate are emulsifying agent.These compounds may be used singly or in combination of two or more.
By using mentioned emulsifier, the latex in the time of can stably keeping letex polymerization improves polymerisation conversion.In addition, as mentioned emulsifier, can use the emulsifying agent identical with the emulsifying agent of the manufacturing that is used for above-mentioned organopolysiloxane (b1-1).
Polymerization temperature when above-mentioned monomer (mm) is carried out polymerization is generally 65 ℃～98 ℃, is preferably 70 ℃～95 ℃.In addition, polymerization time is generally 0.5～6 hour.
The volume average particle size of the compounded rubber (b1) that obtains by above operation is preferably 50～150nm, more preferably 60～120nm.In addition, the ratio of volume average particle size and number average bead diameter is preferably below 2, more preferably below 1.5, is particularly preferably below 1.1.And gel content is preferably more than the 70 quality %, more preferably more than the 90 quality %, is particularly preferably more than the 95 quality %, and the toluene swell degree is preferably 2～30 times, more preferably 6～25 times.
The compounded rubber that obtains as described above (b1) becomes the form that contains from the grafting compound of poly-(methyl) acrylate (b1-2) grafting of the structural unit of above-mentioned monomer (mm) in organopolysiloxane (b1-1), or organopolysiloxane (b1-1) and poly-(methyl) acrylate (b1-2) of containing from the structural unit of above-mentioned monomer (mm) form the cross-linked network that mutually twines, the form that can not be separated from each other in fact.In addition, sometimes in the latex that contains this compounded rubber (b1), contain from poly-(methyl) acrylate (b1-2) of the structural unit of above-mentioned monomer (mm) and organopolysiloxane (b1-1) free and comprise independently.
Above-mentioned compounded rubber (b1), as required can be further with aforesaid propylene acid be rubber polymer (a1) situation similarly, in the hypertrophy processing.
The ethene base system monomer (b2) that is used for the formation of mentioned component [B] contains (methyl) acrylic acid alkyl ester compound, aromatic ethenyl compound and the vinyl cyanide based compound of second-order transition temperature above 0 ℃ of homopolymer.
As second-order transition temperature (methyl) acrylic acid alkyl ester compound above 0 ℃ of homopolymer, can enumerate: methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methyl acrylate etc.
About aromatic ethenyl compound and vinyl cyanide based compound, can be useful in aromatic ethenyl compound and the vinyl cyanide based compound that can use in the above-mentioned ethene base system monomer (a2).
Second-order transition temperature contained, homopolymer surpasses the ratio of (methyl) acrylic acid alkyl ester compound of 0 ℃ in the above-mentioned ethene base system monomer (b2), viewpoint from the balance of the shock resistance of products formed and bright property, be made as in the situation of 100 quality % in the total with (methyl) acrylic acid alkyl ester compound, aromatic ethenyl compound and vinyl cyanide based compound, be preferably 40～60 quality %.
In addition, the ratio of the usage quantity of contained aromatic ethenyl compound and vinyl cyanide based compound in the above-mentioned ethene base system monomer (b2), be made as in the total with both in the situation of 100 quality %, be preferably respectively 10～90 quality % and 10～90 quality %.
Total amount with respect to above-mentioned ethene base system monomer (b2), the ratio of the total amount of (methyl) acrylic acid alkyl ester compound, aromatic ethenyl compound and the vinyl cyanide based compound of second-order transition temperature contained, homopolymer above 0 ℃ is preferably 70～100 quality % in the above-mentioned ethene base system monomer (b2), more preferably 85～100 quality %.
Above-mentioned ethene base system monomer (b2) can be surpassed by the second-order transition temperature of homopolymer (methyl) acrylic acid alkyl ester compound of 0 ℃, aromatic ethenyl compound and vinyl cyanide based compound consist of, and (second-order transition temperature of homopolymer is (methyl) acrylic compound below 0 ℃ also can also to contain other monomers, the maleimide amine compound, unsaturated acid anhydride, contain the carboxyl unsaturated compound, the hydroxyl unsaturated compound, contain amino unsaturated compound, contain the amido unsaturated compound, contain the epoxy group(ing) unsaturated compound, contain Azoles quinoline base unsaturated compound etc.).And, as other monomers, in the situation that contain the maleimide amine compound, with the situation of using acrylic rubber matter polymkeric substance (a1) to make composition [A] similarly, sometimes contain the not graftomer formation of multipolymer conduct from the structural unit of maleimide amine compound, therefore, contain in the situation that the multipolymer from the structural unit of maleimide amine compound generates, this multipolymer is included in the composition [C].
The ratio that is used for the usage quantity of the compounded rubber (b1) of manufacturing of mentioned component [B] and ethene base system monomer (b2), viewpoint from the balance of the shock resistance of products formed and bright property, be made as in the total with both in the situation of 100 quality %, be preferably respectively 30～90 quality % and 10～70 quality %, more preferably 50～85 quality % and 15～50 quality %, more preferably 70～80 quality % and 20～30 quality %.
The manufacture method of mentioned component [B] is not particularly limited, and can be: supply with the part of ethene base system monomer (b2) and carry out polymerization, the method for supplying with thereafter remainder and carrying out polymerization in the presence of compounded rubber (b1); The method etc. of in the presence of compounded rubber (b1), supplying with the total amount of ethene base system monomer (b2) and carrying out polymerization.In the present invention, preferred the former method, particularly, can be in the presence of compounded rubber (b1) second-order transition temperature of homopolymer be surpassed (methyl) acrylic acid alkyl ester compound of 0 ℃ and carry out graft polymerization, add thereafter and do not contain the maleimide amine compound, contain the ethene base system monomer of aromatic ethenyl compound and vinyl cyanide based compound and carry out polymerization.During composition [B] that use obtains by the using method of carrying out like this ethene base system monomer (b2), can access the excellent especially products formed of shock resistance and bright property.
Graft polymerization can be for same with the manufacture method of mentioned component [A].In reaction system, can add as required water, emulsifying agent, polymerization starter, chain-transfer agent etc.These emulsifying agents, polymerization starter, chain-transfer agent etc. can use illustrative compound in the manufacture method of mentioned component [A].
Viewpoint from forming process, shock resistance, bright property etc., percentage of grafting in the mentioned component [B], namely the ratio that contains from the multipolymer of the structural unit of ethene base system monomer (b2) in the upper grafting of compounded rubber (b1) is preferably 5～200 quality %, more preferably 10～150 quality %, more preferably 20～120 quality %.Percentage of grafting is crossed when hanging down, and the shock resistance of products formed is insufficient sometimes.On the other hand, when percentage of grafting was too high, forming process was insufficient sometimes.
Mentioned component [C] is for containing structural unit from the maleimide amine compound (hereinafter referred to as " structural unit (c1) " with respect to the entire infrastructure unit.) 10～70 quality %, preferred 20～70 quality %, the further maleimide based copolymer of preferred 25～65 quality %.The content of said structure unit (c1) can access the products formed of thermotolerance and shock resistance excellence when above-mentioned scope.
In addition, mentioned component [A] for the situation of the graft resin that consisted of by acrylic rubber matter polymkeric substance section and the multipolymer section from the structural unit (c1) of maleimide amine compound of containing and mentioned component [B] situation for the graft resin that consisted of by compounded rubber section and the multipolymer section from the structural unit (c1) of maleimide amine compound of containing under, these graft resins are not included in the composition [C].That is, this composition [C] is for structurally reaching [B] independently composition with mentioned component [A].
In addition, mentioned component [C] can be for containing the only multipolymer of a kind of structural unit (c1), also can be for containing the multipolymer more than 2 kinds.
Mentioned component [C] further contains other structural units (hereinafter referred to as " structural unit (c2) " for containing the multipolymer of structural unit (c1).)。This structural unit (c2) be from can with the structural unit of the ethene base system monomer of maleimide amine compound copolymerization.
As can with the ethene base system monomer of maleimide amine compound copolymerization, can enumerate: aromatic ethenyl compound, vinyl cyanide based compound, unsaturated acid anhydride, (methyl) acrylic compound, contain carboxyl unsaturated compound, hydroxyl unsaturated compound, contain amino unsaturated compound, contain the amido unsaturated compound, contain the epoxy group(ing) unsaturated compound, contain
Figure BDA00002478074600331
Azoles quinoline base unsaturated compound etc.The applicable illustrative compound of ethene base system monomer (a2) as can be used in the formation of mentioned component [A] of these compounds.And these compounds may be used singly or in combination of two or more.
In the present invention, as can with the ethene base system monomer of above-mentioned maleimide amine compound copolymerization, preferably contain aromatic ethenyl compound.
As mentioned component [C], preferred maleimide based copolymer is as described below.
(C1) multipolymer of maleimide amine compound and aromatic ethenyl compound.
(C2) multipolymer of maleimide amine compound, aromatic ethenyl compound and unsaturated acid anhydride.
(C3) multipolymer of maleimide amine compound, aromatic ethenyl compound and vinyl cyanide based compound.
(C4) multipolymer of maleimide amine compound, aromatic ethenyl compound, vinyl cyanide based compound and unsaturated acid anhydride.
(C5) multipolymer of maleimide amine compound, aromatic ethenyl compound and (methyl) acrylic compound.
(C6) multipolymer of maleimide amine compound, aromatic ethenyl compound, (methyl) acrylic compound and unsaturated acid anhydride.
(C7) multipolymer of maleimide amine compound, aromatic ethenyl compound, vinyl cyanide based compound and (methyl) acrylic compound.
(C8) multipolymer of maleimide amine compound, aromatic ethenyl compound, vinyl cyanide based compound, (methyl) acrylic compound and unsaturated acid anhydride.
In above-mentioned form, as the maleimide amine compound, preferred N-phenylmaleimide, as aromatic ethenyl compound, optimization styrene, as the vinyl cyanide based compound, preferred vinyl cyanide, as unsaturated acid anhydride, preferred maleic anhydride.
In the present invention, from the viewpoint of forming process, thermotolerance and molded appearance, the second-order transition temperature of the composition [C] of measuring according to ASTM D3418 is preferably 100 ℃～250 ℃, more preferably 120 ℃～230 ℃.When this second-order transition temperature was too high, forming process, shock resistance became insufficient sometimes, crossed when low when it, sometimes can not obtain fully stable on heating raising effect.
From the viewpoint of forming process and bright property, the limiting viscosity of mentioned component [C] (in the methyl ethyl ketone, 30 ℃) is preferably 0.1～1.5dl/g, more preferably 0.15～1.0dl/g.
Above-mentioned limiting viscosity is adjusted 5 solution that concentration is different by making mentioned component [C] be dissolved in methyl ethyl ketone, obtains 30 ℃ of lower reduced viscositys of measuring each concentration with the Ubbelohde viscosity tube.
The kind of the polymerization starter that above-mentioned limiting viscosity can be used when being adjusted at manufacturing compositions such as utilizing method described later [C], chain-transfer agent, emulsifying agent, solvent etc., amount, polymerization time, polymerization temperature etc. are controlled.
In the present invention, the not graftomer that forms when mentioned component [C] can come comfortable manufacturing mentioned component [A] or composition [B], the multipolymer that also can be combined with other preparation forms.In the latter's the situation, can be use the maleimide amine compound and can with the ethene base system monomer of this maleimide amine compound copolymerization, the material that utilizes known letex polymerization, solution polymerization, mass polymerization etc. to form.
Other manufacture method as mentioned component [C], can enumerate making the ethene base system monomer copolymerization that does not contain the maleimide amine compound, contains unsaturated acid anhydride and aromatic ethenyl compound, make thereafter the multipolymer that obtains and ammonia and/or primary amine reaction (hereinafter referred to as " imidization reaction ".), manufacturing contains the method for the multipolymer of structural unit (c1).
As the primary amine that is used for above-mentioned imidization reaction, can enumerate: methylamine, ethamine, propylamine, butylamine, hexylamine, hexahydroaniline, decyl amine, aniline, Tolylamine, naphthylamines, chloroaniline, dichlorphenamide bulk powder, bromaniline, dibromo aniline etc.Wherein, aniline particularly preferably.
Above-mentioned imidization reaction can be used autoclave, carries out with solution state, bulk state or suspended state.In addition, also can use the melting mixing devices such as screw extrusion press, under molten state, react.
Carry out with solution state in the situation of above-mentioned imidization reaction, the solvent of use is not particularly limited, and can enumerate: the ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone; Tetrahydrofuran (THF), Isosorbide-5-Nitrae-two
Figure BDA00002478074600351
The ethers such as alkane; The aromatic hydrocarbons such as toluene, dimethylbenzene; Dimethyl formamide, dimethyl sulfoxide (DMSO), METHYLPYRROLIDONE etc.
The temperature of reaction of above-mentioned imidization is preferably 50 ℃～350 ℃, more preferably 100 ℃～300 ℃.
Above-mentioned imidization reaction may not need the existence of catalyzer.Use in the situation of catalyzer preferred Trimethylamine 99, triethylamine, Tributylamine, DMA, N, the tertiary amines such as N-Diethyl Aniline.
Mentioned component [C] can be used singly or in combination of two or more.
Below, in composition of the present invention for the structural unit that is selected from from aromatic ethenyl compound as containing of any composition (below be also referred to as " structural unit (d1) ".), from the structural unit of vinyl cyanide based compound (below be also referred to as " structural unit (d2) ".) and from the structural unit of (methyl) acrylic acid alkyl ester compound (below be also referred to as " structural unit (d3) ".) at least a kind of structural unit and the composition [D] that does not contain from the polymkeric substance of the structural unit of maleimide amine compound describe.
In addition, this composition [D] can contain from unsaturated acid anhydride, contains carboxyl unsaturated compound, hydroxyl unsaturated compound, contains amino unsaturated compound, contains the amido unsaturated compound, contains the epoxy group(ing) unsaturated compound, contain The structural unit of azoles quinoline base unsaturated compound etc.
Above-mentioned aromatic ethenyl compound, vinyl cyanide based compound, (methyl) acrylic compound, unsaturated acid anhydride, contain carboxyl unsaturated compound, hydroxyl unsaturated compound, contain amino unsaturated compound, contain the amido unsaturated compound, contain the epoxy group(ing) unsaturated compound and contain
Figure BDA00002478074600353
The applicable illustrative compound of ethene base system monomer (a2) as can be used in the formation of mentioned component [A] of azoles quinoline base unsaturated compound.And these compounds may be used singly or in combination of two or more.
At mentioned component [A] for by acrylic rubber matter polymkeric substance section with do not contain structural unit (c1) from the maleimide amine compound, contain said structure unit (d1), (d2), the situation of the graft resin that (being total to) polymkeric substance section (d3) etc. consists of and mentioned component [B] are for by compounded rubber section with do not contain structural unit (c1) from the maleimide amine compound, contain said structure unit (d1), (d2), in the situation of the graft resin that (being total to) polymkeric substance section (d3) etc. consists of, these graft resins are not included in the composition [D].That is, this composition [D] is for structurally reaching [B] independently composition with mentioned component [A].
In the situation that composition of the present invention contains composition [D], the appearance of the products formed that can make the forming process excellence, obtains and the products formed of shock resistance excellence.
As mentioned component [D], below carry out illustration.
(D1) by structural unit (d1) with the multipolymer (multipolymer of aromatic ethenyl compound and vinyl cyanide based compound) that (d2) consists of.
(D2) by structural unit (d1) with the multipolymer that (d3) consists of (multipolymer of aromatic ethenyl compound and (methyl) acrylic compound).
(D3) by structural unit (d1), (d2) and the multipolymer (multipolymer of aromatic ethenyl compound, vinyl cyanide based compound and (methyl) acrylic compound) that (d3) consists of.
(D4) (being total to) polymkeric substance ((being total to) polymkeric substance of (methyl) acrylic compound) that is consisted of by structural unit (d3).
Wherein, from the viewpoint of forming process, appearance and shock resistance, particularly preferably form (D1) reaches multipolymer (D3).
In addition, mentioned component [D] is in the situation of multipolymer of above-mentioned form (D1), structural unit (d1) and containing (d2) are proportional, be made as in the total with both in the situation of 100 quality %, be preferably respectively 50～95 quality % and 5～50 quality %, more preferably 60～95 quality % and 5～40 quality %.
Mentioned component [D] is in the situation of multipolymer of above-mentioned form (D3), structural unit (d1), (d2) and containing (d3) are proportional, be made as in the total with them in the situation of 100 quality %, be preferably respectively 5～45 quality %, 5～45 quality % and 10～80 quality %, more preferably 10～30 quality %, 10～30 quality % and 40～80 quality %.
From the thermotolerance of forming process, the products formed that obtains and the viewpoint of appearance, the limiting viscosity of mentioned component [D] (in the methyl ethyl ketone, 30 ℃) is preferably 0.1～1.5dl/g, more preferably 0.15～1.0dl/g.
The limiting viscosity of mentioned component [D] can similarly be obtained with the limiting viscosity of mentioned component [C].
The kind of the polymerization starter that above-mentioned limiting viscosity can be used when being adjusted at manufacturing compositions such as utilizing method described later [D], chain-transfer agent, emulsifying agent, solvent etc., amount, polymerization time, polymerization temperature etc. are controlled.
In the present invention, the not graftomer that forms when mentioned component [D] can come comfortable manufacturing mentioned component [A] or composition [B] also can cooperate the multipolymer of other preparation.In the latter's the situation, can use and contain at least a kind the ethene base system monomer that is selected from aromatic ethenyl compound, vinyl cyanide based compound and (methyl) acrylic acid alkyl ester compound, utilize the formation such as known letex polymerization, solution polymerization, mass polymerization.
Mentioned component [D] can be used singly or in combination of two or more.
As mentioned above, composition of the present invention can be made the composition that does not contain composition [D], and therefore, preferred composition is the composition that contains composition [A], [B], [C] and [D], and the composition that contains composition [A] [B] and [C].These compositions can further contain other thermoplastic resins described later, additive etc.
Composition of the present invention contains in the situation of other thermoplastic resins, the upper limit of its content is made as in the situation of 100 mass parts in the total amount with mentioned component [A], [B], [C] and [D], is preferably 30 mass parts, more preferably 20 mass parts, more preferably 10 mass parts.
In composition of the present invention, aforesaid propylene acid is the total of the content of the content of rubber polymer (a1) and above-mentioned compounded rubber (b1), be made as in the situation of 100 quality % in the total with mentioned component [A], [B], [C] and [D], be 8～35 quality %, be preferably 12～32 quality %, more preferably 15～28 quality %.The ratio of above-mentioned total amount can access the excellent products formed such as thermotolerance, shock resistance, molded appearance when above-mentioned scope.
In addition, in composition of the present invention, content from the structural unit of maleimide amine compound, be made as in the situation of 100 quality % in the structural unit that will consist of mentioned component [A], the structural unit that consists of mentioned component [B], the total that consists of the structural unit of mentioned component [C] and consist of the structural unit of mentioned component [D], be 5～30 quality %, be preferably 5～25 quality %, more preferably 8～25 quality % are particularly preferably 8～20 quality %.The content of said structure unit can access the excellent products formed such as thermotolerance, molded appearance, bright property when above-mentioned scope.
In addition, the such content of 5～30 quality % is preferably only from composition [C], but also can be from composition [C] and composition [A] and/or composition [B].Example as the latter, be following situation: composition [A] carries out the graft resin that polymerization obtains for the ethene base system monomer (a2) that will contain aromatic ethenyl compound and vinyl cyanide based compound and maleimide amine compound in the presence of acrylic rubber matter polymkeric substance (a1), and the situation from the structural unit of maleimide amine compound is contained in the multipolymer section in this graft resin; And composition [B] carries out the graft resin that polymerization obtains for the ethene base system monomer (b2) that will contain aromatic ethenyl compound and vinyl cyanide based compound and maleimide amine compound in the presence of compounded rubber (b1), and the situation from the structural unit of maleimide amine compound is contained in the multipolymer section in this graft resin.
And, in composition of the present invention, containing of the compounded rubber (b1) of the content of the acrylic rubber matter polymkeric substance (a1) of formation mentioned component [A] and formation mentioned component [B] is proportional, be made as in the total with both in the situation of 100 quality %, be preferably respectively 10～95 quality % and 5～90 quality %, more preferably 20～90 quality % and 10～80 quality %.By being set as aforementioned proportion, the shock resistance of products formed and bright property are excellent, the generation of the wire drawing when the inhibition vibration is deposited.
In composition of the present invention, the total of the content of the content of mentioned component [A] and mentioned component [B], viewpoint from shock resistance, thermotolerance, molded appearance and the bright property of the forming process of composition and products formed, be made as in the situation of 100 quality % in the total with mentioned component [A], [B], [C] and [D], be preferably 10～90 quality %, more preferably 15～70 quality % are particularly preferably 20～60 quality %.
In composition of the present invention, the ratio of the content of mentioned component [C], viewpoint from shock resistance, thermotolerance, molded appearance and the bright property of products formed, be made as in the situation of 100 quality % in the total with mentioned component [A], [B], [C] and [D], be preferably 10～90 quality %, more preferably 15～70 quality % are particularly preferably 15～60 quality %.
Lampshade of the present invention contains in the situation of mentioned component [D] with the thermoplastic resin composition, the ratio of the content of this composition [D], be made as in the situation of 100 quality % in the total with mentioned component [A], [B], [C] and [D], be preferably below the 80 quality %, more preferably 15～70 quality % are particularly preferably 20～65 quality %.When the content of mentioned component [D] surpassed 80 quality %, thermotolerance and shock resistance became insufficient sometimes.
Composition of the present invention contains in the situation of mentioned component [D], viewpoint from thermotolerance, shock resistance and the aesthetic appearance of the forming process of composition and products formed, the limiting viscosity of the mixture of mentioned component [C] and [D] (in the methyl ethyl ketone, 30 ℃) is preferably 0.2～1.2dl/g, more preferably 0.25～1.0dl/g, more preferably 0.3～0.8dl/g.
The mixture of mentioned component [C] and [D] is for being equivalent to the not composition of graftomer in composition of the present invention.In the situation that reclaim these compositions, applicable with in the composition input acetone of the present invention, after using bobbing machine vibration (23 ℃, 2 hours), use separating centrifuge to carry out centrifugation (0 ℃ of temperature, revolution 28,000rpm, 1 hour), the method etc. of removing thereafter acetone from the solvable composition of acetone that reclaims.Regenerant after acetone is removed is called as " acetone soluble polymer ".
The limiting viscosity of acetone soluble polymer can similarly be obtained with the limiting viscosity of mentioned component [C].
In the present invention, preferred composition for the raw material that will contain following component (below be also referred to as " raw material [R] ".) mix and the composition that obtains (hereinafter referred to as " composition [X] ".), described component is: [S] contain aforesaid propylene acid be rubber polymer (a1) in the presence of, the ethene base system monomer that does not contain the maleimide amine compound, comprises aromatic ethenyl compound and vinyl cyanide based compound carried out polymerization and the rubber reinforced resin of the acrylic rubber matter enhancing by polymer graft resin that obtains (below be also referred to as " raw material [S] ".), [T] contains in the presence of above-mentioned compounded rubber (b1), (methyl) acrylic acid alkyl ester compound that the second-order transition temperature of homopolymer is surpassed 0 ℃ is carried out polymerization, the ethene base system monomer that then will not contain the maleimide amine compound, comprises aromatic ethenyl compound and vinyl cyanide based compound carry out polymerization and the compounded rubber that obtains strengthen graft resin rubber reinforced resin (below be also referred to as " raw material [T] ".), and [U] with respect to the entire infrastructure unit contain 10～70 quality % from the maleimide based copolymer of the structural unit of maleimide amine compound (below be also referred to as " raw material [U] ".)。
Above-mentioned raw materials [R] and composition [X] can contain other thermoplastic resins and additive.
In above-mentioned raw materials [R], raw material [S] is for to contain in the presence of acrylic rubber matter polymkeric substance (a1), and the ethene base system monomer that does not contain the maleimide amine compound, comprises aromatic ethenyl compound and vinyl cyanide based compound (can be contained (methyl) acrylic acid alkyl ester compound.) carry out polymerization and the acrylic rubber matter enhancing by polymer graft resin that obtains (below be also referred to as " graft resin (Ar) ".), and contain from the structural unit of aromatic ethenyl compound and from the multipolymer of the structural unit of vinyl cyanide based compound and (can contain the structural unit from (methyl) acrylic acid alkyl ester compound.Below be also referred to as " multipolymer (Dr1) ".) rubber reinforcement aromatic vinyl base system resin.Wherein, graft resin (Ar) is equivalent to composition [A], and multipolymer (Dr1) is equivalent to composition [D].
Above-mentioned raw materials [T] surpasses (methyl) acrylic acid alkyl ester compound of 0 ℃ and carries out polymerization for containing in the presence of compounded rubber (b1) second-order transition temperature with homopolymer, then will not contain the maleimide amine compound, the ethene base system monomer that comprises aromatic ethenyl compound and vinyl cyanide based compound carries out polymerization and the compounded rubber that obtains strengthens the rubber reinforced resin of graft resin, usually, the multipolymer of above-mentioned each monomer contain the compounded rubber that the upper grafting of above-mentioned compounded rubber (b1) forms strengthen graft resin (below be also referred to as " graft resin (Br) ".) and comprise from the structural unit of aromatic ethenyl compound and from the multipolymer of the structural unit of vinyl cyanide based compound and (can contain the structural unit from (methyl) acrylic acid alkyl ester compound.Below be also referred to as " multipolymer (Dr2) ".)。Wherein, graft resin (Br) is equivalent to composition [B], and multipolymer (Dr2) is equivalent to composition [D].
In addition, raw material [U] is maleimide based copolymer contained in the mentioned component [C], can directly use pre-prepd maleimide based copolymer.
Above-mentioned composition [X], as polymkeric substance or resin contained in the above-mentioned raw materials [R], in the situation of using the composition that above-mentioned raw materials [S], [T] and [U] obtain, the ratio of the content of these in the above-mentioned raw materials [R], 3 total is being made as in the situation of 100 quality %, be preferably respectively 1～89 quality %, 1～89 quality % and 10～90 quality %, more preferably 8～50 quality %, 2～40 quality % and 10～90 quality % are particularly preferably 8～42 quality %, 2～30 quality % and 28～90 quality %.By in above-mentioned scope, using each composition, can access the products formed of thermotolerance, shock resistance, molded appearance, the deposited property of vibration and bright property excellence.
In addition, above-mentioned raw materials [R] also can be combined with in addition be equivalent to mentioned component [D] (being total to) polymkeric substance (hereinafter referred to as " (being total to) polymkeric substance [V] ".)。As this (being total to) polymkeric substance [V], can use as mentioned component [D] illustrative (being total to) polymkeric substance.These may be used singly or in combination of two or more.
Above-mentioned composition [X], as polymkeric substance or resin contained in the above-mentioned raw materials [R], for using above-mentioned raw materials [S], in the situation of the composition that [T] and [U] and (being total to) polymkeric substance [V] obtain, the ratio of these usage quantity, 4 total is being made as in the situation of 100 quality %, be preferably respectively 1～88 quality %, 1～88 quality %, 10～89 quality % and 1～80 quality %, 8～50 quality % more preferably, 2～40 quality %, 10～40 quality % and 5～60 quality % are particularly preferably 8～42 quality %, 2～30 quality %, 10～40 quality and 20～50 quality %.By in above-mentioned scope, using each composition, can access the products formed of thermotolerance, shock resistance, molded appearance, the deposited property of vibration and bright property excellence.
Above-mentioned composition [X] mixes raw material [R] and obtains, utilizing identical polymerization process to obtain in the situation of raw material [S], [T] and [U] (and (being total to) polymkeric substance [V]), can be formed in latex or the resin solution and reach (Dr2) resin compound of (and (being total to) polymkeric substance [V]) formation by graft resin (Ar), graft resin (Br), raw material [U], multipolymer (Dr1), can make the composition that its recovery is obtained.
The form of composition of the present invention is not particularly limited, and is preferably the melting mixing thing.Therefore, in the situation that above-mentioned composition [X] is made the melting mixing thing, the applicable method of above-mentioned raw materials [R] being used mixing rolls such as single screw extrusion machine, twin screw extruder, Banbury mixer, pressurization kneader and (two) roller etc. etc.When mixing, can each composition that consist of above-mentioned raw materials [R] is once mixing, while it is mixing also can to separate cooperation.In addition, after usefulness Banbury mixer, kneader etc. are mixing, also can utilize the forcing machine granulation.Melting temperature is preferably 200 ℃～300 ℃, more preferably 220 ℃～280 ℃.
In composition of the present invention, as other thermoplastic resins that can cooperate, can enumerate: in the presence of other rubber polymers except acrylic rubber matter polymkeric substance (a1) and compounded rubber (b1), ethene base system monomer carried out polymerization and rubber reinforced resin, polyamide resin, polycarbonate resin, vibrin, the polyphenylene oxide resin etc. such as the ABS resin that obtains, AES resin.These can contain separately, also can contain more than 2 kinds.
In composition of the present invention, as the additive that can cooperate, can enumerate: weighting agent, metal-powder, toughener, softening agent, compatilizer, thermo-stabilizer, photostabilizer, antioxidant, UV light absorber, pigment, static inhibitor, lubricant, fire retardant, antiseptic-germicide etc.
Lampshade of the present invention is preferably the molding material that forms the products formed of evaporation layer by direct evaporation on its surface with the thermoplastic resin composition.Directly evaporation is for arranging undercoat, directly passes through the method for the evaporation layer of formation metals such as vacuum vapour deposition, sputtering method etc. on the surface of products formed.
As the concrete method of direct evaporation, for example, be decompressed to 10 -3～10 -4In the container about Pa products formed is set, makes the deposition material that in this container, gasifies or distil be attached to the surface of products formed, form the evaporation layer.In the situation that make deposition material gasification or distillation, can suitably select the known means such as resistive heating, high-frequency induction.In addition, as deposition material, except the metals such as aluminium, chromium, zinc, gold and silver, platinum, nickel, can use metal oxide etc.In addition, also can make in advance to the products formed before the evaporation processing of adaptation raising by RF plasma body, ion gun irradiation etc., according to composition of the present invention, can omit to the products formed that obtains this processing.
In addition, lampshade of the present invention is preferably the molding material of the products formed of the deposited method of applicable vibration with the thermoplastic resin composition.
Vibrating deposited method is following method: use composition of the present invention to form a resin component, after using composition of the present invention or other compositions to form another resin component such as lamp lens, the vibration that face is exerted pressure and back and forth movement causes that the wish of 2 resin components is engaged, by its heat of friction, with bonding resinous principle melting with the position, both are engaged.
As other compositions, can make thermoplastic resin composition of containing polycarbonate resin, polymethylmethacrylate etc. etc.
According to composition of the present invention, in the situation that make between the products formed vibration deposited, suppress the generation of wire drawing, therefore do not damage the aesthetic appearance of joint product.
The products formed (lampshade etc.) that products formed of the present invention obtains for the composition that uses the invention described above.That is, products formed of the present invention contains the composition of the invention described above.
Because the forming process of composition is excellent, therefore be suitable for injection moulding, sheet material extrusion moulding, vacuum forming, special-shaped extrusion moulding, compressed moulding method, slush molding method, differential pressure forming method, blow molding method, foaming method, the gas inject method of forming etc.
In addition, to products formed of the present invention, do not carry out to have implemented utilize the directly metalized of vapour deposition methods such as vacuum vapour deposition, sputtering method to its surface in the situation of formation etc. of undercoat.
Carried out the products formed of metalized, its bright property is excellent.And this surface can be former state, but for the generation of the scar protecting it to avoid to cause such as dust etc., oxidative degradation etc., can form finishing coat by application, plasma polymerization etc.
Embodiment
Below, enumerate embodiment, illustrate in greater detail the present invention, but only otherwise exceed main idea of the present invention, the present invention is not limited to described embodiment.In addition, in following, as long as no specified otherwise, part and % are quality criteria.
1. evaluation method
With physical property and to estimate relevant measuring method as described below.
(1) particle diameter of acrylic rubber matter polymkeric substance and size distribution thereof
The volume average particle size (Mv) of the acrylic rubber matter polymkeric substance in the latex and number average bead diameter (Mn) use HONEYWELL society system " マ イ Network ロ ト ラ ッ Network UPA150 ", under 25 ℃, measure.Unit is nm.Calculate size distribution Mv/Mn by this measured value.
(2) toluene swell degree and the gel content of acrylic rubber matter polymkeric substance
The following method of toluene swell degree and gel content utilization is obtained.
Approximately 0.2 gram of weighing acrylic rubber matter polymkeric substance (is designated as Wr with quality.), drop among the toluene 25ml, stir lightly.25 ℃ lower place 48 hour, use 200 purpose wire nettings of in advance weighing (quality be designated as Wm gram thereafter.) filter, be separated into insoluble minute and solvable minute.After the separation, rapidly with the wire netting weighing with filtering separation in insoluble minute (quality is designated as the W1 gram), deducted the weighing value (Wm) of wire netting by this weighing value (W1), insoluble minute the weighing value that obtains with toluene swell (is designated as the Ws gram with quality.)。Then owing to containing toluene with in insoluble minute of toluene swell, therefore with its 25 ℃ lower air-dry 12 hours, continue to use Vacuumdrier 60 ℃ of lower dryings 12 hours, thus contained toluene drying in insoluble minute is removed.(quality was designated as the W2 gram with dried insoluble minute with the wire netting weighing.), being deducted the weighing value (Wm) of wire netting by this weighing value (W2), the dry weight that obtains insoluble minute (is designated as the Wd gram with quality.)。Utilize following formula to calculate gel content and toluene swell degree by these weighing values.
Gel content (quality %)=[Wd (g)/Wr (g)] * 100
＝[{W2(g)-Wm(g)}/Wr(g)]×100
Toluene swell degree (doubly)=Ws (g)/Wd (g)
＝[W1(g)-Wm(g)]/[W2(g)-Wm(g)]
In addition, the acrylic rubber matter polymkeric substance of be used for measuring on one side drips the latex that contains above-mentioned polymkeric substance for stirring 15% calcium chloride water, polymkeric substance is solidified and wash, drying and the solid rubber that obtains.
(3) percentage of grafting
In a certain amount of (x gram) input acetone with the rubber reinforced resin (S) that uses acrylic rubber matter polymkeric substance to obtain, use bobbing machine vibration 2 hours, make free (being total to) polymkeric substance (not graftomer=acetone soluble polymer) dissolving.This liquid is used centrifuge separator thereafter,, with 28,000rpm centrifugation 1 hour.The insoluble throw out that obtains is used Vacuumdrier, descended insoluble minute (graft resin) (y gram) of weighing dry 2 hours at 120 ℃.When the amount of contained acrylic rubber matter polymkeric substance is designated as the xr gram in the x gram with above-mentioned rubber reinforced resin (S), utilize following formula to calculate percentage of grafting.Replace acrylic rubber matter polymkeric substance, the situation of the rubber reinforced resin (T) that the use compounded rubber obtains is calculated similarly.
Percentage of grafting (%)=[(y-xr) ÷ xr] * 100
(4) limiting viscosity
To the rubber reinforced resin (T) that obtains among the rubber reinforced resin (S) that obtains among synthesis example 2-1～2-11 and the synthesis example 2-12, measure the not limiting viscosity of graftomer (acetone soluble polymer).In addition, also measure by material composition is the mixing and limiting viscosity acetone soluble polymer that composition that obtain obtains.Unit is dl/g.
(5) Charpy shock strength
Measure according to ISO179.Loading is 2J, and unit is kJ/m 2
(6) loading deflection temperature
Measure according to ISO75.Unit is ℃.
(7) appearance (current mark, color spot, gloss)
When estimating surperficial aesthetic appearance, as tinting material, use composition with respect to record in the table further to cooperate 0.2 part of Sakai chemistry society's calcium stearate processed " SC-100 " (trade(brand)name) and the charcoal processing of Mitsubishi Chemical society to deceive 0.5 part of " RCF-#45 " (trade(brand)name) and the composition that obtains.
Said composition is supplied to a day smart Resin Industry society electric injection moulding machine processed " エ Le ジ ェ Network ト NEX30 " (trade(brand)name), carry out injection molding (220 ℃～260 ℃ of resin temperatures, 50 ℃ of die temperatures), obtain the flat black products formed (central authorities on the limit of 55mm have the side gate of 4mm * 1mm) of 80mm * 55mm * 2.4mm.
Aesthetic appearance is judged with following benchmark in the surface of this products formed of visual observation.
◎: gloss is excellent, does not see current mark and color spot.
Zero: gloss is good, does not almost see current mark and color spot.
△: gloss is poor a little, sees some current marks and color spot.
*: gloss is insufficient, sees current mark and color spot.
(8) vibrate deposited property (powder and wire drawing)
The black combination of appearance that will above-mentioned for estimating (7) is supplied with toshiba machine society injection moulding machine processed " IS-170FA " (model name), carry out injection molding (220 ℃～260 ℃ of resin temperatures), the lampshade 12 that has peristome on curved surface is carried out moulding (with reference to Fig. 2).The unit of the size in the accompanying drawing is " mm ".
On the other hand, as by adhesion material, mitsubishi rayon society metha crylic resin processed " ア Network リ ペ ッ ト VH-4 " (trade(brand)name) is supplied with injection moulding machine, carry out injection molding (220 ℃～270 ℃ of resin temperatures), obtain the lamp lens 11 (with reference to Fig. 1) of regulation shape.
Thereafter, lamp lens 11 and lampshade 12 are utilized the moving cladding machine " BURANSON2407 " (model name) of Japanese エ マ ソ Application society's damping, vibrate according to Fig. 3 deposited.Fig. 3 is the accompanying drawing at deposited position of 2 parts of expression, under the following conditions, carries out the circumference of the peristome of the lampshade 12a of the downward jut of the lamp lens 11a of A-A ' the line section in the presentation graphs 1 and B-B ' the line section in the presentation graphs 2 deposited.Vibrate when deposited the radical (radical of the thread wire drawing more than the 2mm that in lampshade, produces) of the number of counting tree cosmetics body (in lampshade, produce and can by the number of the resin powder about tens of micron～2mm of Visual Confirmation) and wire drawing at this.By the number of these resin powders and the radical of wire drawing, based on following benchmark, judge " vibrating deposited property ".
Zero: the number of resin powder is below 5.The wire drawing number is below 5.
△: the number of resin powder is 6～10.The wire drawing number is 6～10.
*: the number of resin powder is more than 11.The wire drawing number is more than 11.
＜vibrate deposited condition＞
(i) the deposited condition of powder amount evaluation usefulness
Sheet amplitude 0.5mm
Initial stage pressure 2.0bar
Initial stage time of vibration 4.0 seconds
Second segment pressure 4.0bar
Second segment time of vibration 2.0 seconds
(ii) the deposited condition of wire drawing amount evaluation usefulness
Sheet amplitude 0.5mm
Initial stage pressure 5.0bar
Initial stage time of vibration 0.5 second
Second segment pressure 5.0bar
Second segment time of vibration 2.0 seconds.
(9) bright property
Appearance that will above-mentioned for estimating (7) black combination supply with toshiba machine society injection moulding machine processed " IS-170FA " (model name), carry out injection molding (220 ℃～260 ℃ of resin temperatures), obtain the lampshade of regulation shape.Then, formed the vapor-deposited film of the aluminium of thickness 120nm by sputter on the surface of this lampshade., on the surface of this vapor-deposited film form the plasma polymerization film of HMDS (1,1,1,3,3,3-hexamethyldisilazane), obtained bright property evaluation formed body thereafter.Sputtering condition and plasma polymerization condition are as described below.
＜sputtering condition＞
The new bright and industrial society vacuum film formation apparatus processed " VRSP350MD " (model name) of device
Pressure 5.0Pa after thick traction finishes
Pressure 5.0 * 10 after main traction finishes -3Pa
Import gas argon gas 100sccm
Vacuum tightness 0.7Pa during film forming
＜plasma polymerization condition＞
Import gas HMDS 30sccm
Vacuum tightness 1.5Pa during polymerization
To the bright property evaluation formed body that obtains, use Tokyo electricity look society's system numeral albedometer " TR-1100AD " (model name) to measure diffuse reflectance.Unit is %.
2. manufacturing raw material
2-1. acrylic rubber matter synthetic polymer
At first, acrylic rubber matter synthetic polymer method for the manufacture of acrylic rubber matter enhancing by polymer graft resin is shown.
Synthesis example 1-1
(1) preparation of liquid
N-butyl acrylate (is designated hereinafter simply as " BA ".) 91.3 parts and allyl methacrylate(AMA) (be designated hereinafter simply as " AMA ".) 0.7 part mix preparation monomer mixture (I).
In addition, in 99 parts in water, dissolve Potassium Persulphate and (be designated hereinafter simply as " KPS ".) 1 part, the preparation polymerization starter aqueous solution (below be abbreviated as " the OXI aqueous solution (I) ".)。
(2) the 1st polymerization process
In the glass reactor processed with whipping appts, raw material and assistant feeding device, thermometer, heating unit etc., pack into 150 parts in water, as the Sodium dodecylbenzene sulfonate of emulsifying agent (below be abbreviated as " SDBS ".) 0.5 part and BA8 part.Thereafter, on one side in the stirring system, under nitrogen gas stream, reaction system is heated on one side.When internal temperature reaches 65 ℃, add in the reactor as electrolytical V-Brite B (below be abbreviated as " PHS ".) 0.03 part, thereafter, reaction system is heated.
When internal temperature reached 75 ℃, 7 parts of the OXI aqueous solution of packing into (I) were in synthermal lower beginning polymerization.In the moment beginning from polymerization through 1 hour, finish the reaction of the 1st polymerization process.In addition, the polymerisation conversion the when reaction of the 1st polymerization process finishes is 96.2%, and the volume average particle size (Mv) of the rubber polymer particle in the latex that obtains is 61nm.
(3) the 2nd polymerization process
In containing the reactor of above-mentioned latex, add 7 parts of 1/3rd and the OXI aqueous solution (I) of monomer mixture (I), under 75 ℃, begin polymerization.After beginning 1 hour from polymerization, when the internal temperature of reactor reaches 75 ℃, further supply with 7 parts of 1/3rd and the OXI aqueous solution (I) of monomer mixture (I), proceed polymerization.It is after 1 hour, and when the internal temperature of reactor reached 75 ℃, 7 parts of the monomer mixture (I) of supply residue 1/3rd and the OXI aqueous solution (I) were proceeded polymerization.It finished polyreaction after 1 hour, obtained containing the latex of acrylic rubber matter polymkeric substance (a1-1).
Polymerisation conversion when the reaction of the 2nd polymerization process finishes is 99.6%, and the volume average particle size (Mv) of the acrylic rubber matter polymkeric substance (a1-1) in the latex that obtains is 133nm, and size distribution Mv/Mn is 1.03.In addition, the toluene swell degree is 15, and gel content is 90.0%.Result more than shown in the table 1.
Synthesis example 1-2
In the 1st polymerization process, except adding 0.5 part of sodium bicarbonate, similarly obtain containing the latex of acrylic rubber matter polymkeric substance (a1-2) with synthesis example 1-1.
Polymerisation conversion when the 1st polymerization process finishes is 97.1%, the volume average particle size (Mv) of the rubber polymer particle in the latex that obtains is 75nm, volume average particle size (Mv) when the 2nd polymerization process finishes is 157m, and size distribution Mv/Mn is 1.04.In addition, the toluene swell degree is 21, and gel content is 82.0%.Result more than shown in the table 1.
Synthesis example 1-3
(1) preparation of liquid
BA79 part and AMA1 part are mixed preparation monomer mixture (II).
In addition, in 10 parts in water, dissolve Calcium Disodium Versenate (below be abbreviated as " EDTA ".) 0.01 part, ferrous sulfate (and below be abbreviated as " FES ".) 0.002 part and rongalite (and below write a Chinese character in simplified form hydrogen and be " NFS ".) 0.3 part, preparation sulfoxylic acid hydrogen salt be the reductive agent aqueous solution (below be abbreviated as " the SFS aqueous solution (I) ".)。
And, dissolved hydrogen dicumyl peroxide in 30 parts in water (below be abbreviated as " CHP ".) 0.025 part, the preparation polymerization starter aqueous solution (below be abbreviated as " the CAT aqueous solution (I) ".)。
(2) the 1st polymerization process
In the glass reactor processed with whipping appts, raw material and assistant feeding device, thermometer, heating unit etc., add 300 parts of entry, SDBS2.0 part and BA20 part.Thereafter, on one side under nitrogen gas stream, reaction system is heated on one side in the stirring system.When internal temperature reaches 60 ℃, in reactor, add 85% minute and 30% minute of the CAT aqueous solution (I) of the SFS aqueous solution (I), in synthermal lower beginning polymerization.In the moment beginning from polymerization through 1 hour, finish the reaction of the 1st polymerization process.In addition, the polymerisation conversion the when reaction of the 1st polymerization process finishes is 98.5%, and the volume average particle size (Mv) of the rubber polymer particle in the latex that obtains is 51nm.
(3) the 2nd polymerization process
The residue 15% minute that in containing the reactor of above-mentioned latex, adds the SFS aqueous solution (I), thereafter at once, all through 1 hour 30 minutes the continuous adding monomer mixture (II) 70% minute and 40% minute of the CAT aqueous solution (I), the beginning polymerization.During this time, the internal temperature of reactor remains on 60 ℃.After adding end, synthermal lower slaking 30 minutes.Thereafter (begin 2 hour from polymerization after), all through 1 hour the continuous adding monomer mixture (II) residue 30% minute and the residue of the CAT aqueous solution (I) 30% minute, proceed polymerization.Add and finish afterwards (after beginning 3 hours from polymerization), after 1 hour, finish polyreaction in synthermal lower slaking, obtain containing the latex of acrylic rubber matter polymkeric substance (a1-3).
Polymerisation conversion when the reaction of the 2nd polymerization process finishes is 96.7%, and the volume average particle size (Mv) of the acrylic rubber matter polymkeric substance (a1-3) in the latex that obtains is 93nm, and size distribution Mv/Mn is 1.06.In addition, the toluene swell degree is 7, and gel content is 98.5%.Result more than shown in the table 1.
Synthesis example 1-4
(1) preparation of liquid
BA99.8 part and AMA0.2 part are mixed preparation monomer mixture (III).
In addition, as the polymerization starter aqueous solution, use the OXI aqueous solution (I) identical with synthesis example 1-1.
And, in 99 parts in water, dissolve not 1 part of homogenizing potassium rosinate soap and KPS1 part, the preparation polymerization starter aqueous solution (below be abbreviated as " the OXI aqueous solution (II) ".)。
(2) the 1st polymerization process
In the glass reactor processed with whipping appts, raw material and assistant feeding device, thermometer, heating unit etc., pack into 170 parts in water, semi-harden tallow fatty acids soda soap (below be abbreviated as " SSF ".) 0.03 part, the sodium salt of beta-naphthalenesulfonic-acid formalin polycondensate (and below be abbreviated as " PNF salt ".) 1.0 parts, as 1.0 parts of electrolytical sodium bicarbonates and monomer mixture (III) 10% minute.Thereafter, on one side under nitrogen gas stream, internal temperature is warming up to 65 ℃ on one side in the stirring system.When reaching 65 ℃, add PHS0.005 part, thereafter, reaction system is heated.
When internal temperature reaches 75 ℃, add the OXI aqueous solution (I) 7 parts, in synthermal lower beginning polymerization.In the moment beginning from polymerization through 1 hour, finish the reaction of the 1st polymerization process.In addition, the polymerisation conversion the when reaction of the 1st polymerization process finishes is 96.8%, and the volume average particle size (Mv) of the rubber polymer particle in the latex that obtains is 112nm.
(3) the 2nd polymerization process
In containing the reactor of above-mentioned latex, all through 4 hours the continuous adding monomer mixture (III) residue 90% minute and 10 parts of the OXI aqueous solution (II), the beginning polymerization.During this time, the temperature of reaction system remains on 75 ℃.After add finishing, the temperature of reaction system was warming up to 80 ℃ with 30 minutes.Then, slaking is 1 hour under this temperature, finishes polyreaction, obtains containing the latex of acrylic rubber matter polymkeric substance (a1-4).
Polymerisation conversion when the reaction of the 2nd polymerization process finishes is 97.7%, and the volume average particle size (Mv) of the acrylic rubber matter polymkeric substance (a1-4) in the latex that obtains is 192nm, and size distribution Mv/Mn is 1.09.In addition, the toluene swell degree is 32, and gel content is 41%.Result more than shown in the table 1.
Synthesis example 1-5
In the 1st polymerization process, making the usage quantity that adds the SDBS in the reactor is 0.1 part, in addition, and is used as 1.5 parts in electrolytical PHS0.03 part and yellow soda ash, in addition, similarly obtain containing the latex of acrylic rubber matter polymkeric substance (a1-5) with synthesis example 1-1.Polymerisation conversion when the 1st polymerization process finishes is 96.8%, the volume average particle size (Mv) of the acrylic rubber matter polymkeric substance (a1-5) in the latex that obtains is 146nm, volume average particle size (Mv) when the 2nd polymerization process finishes is 222m, and size distribution Mv/Mn is 1.09.In addition, the toluene swell degree is 18, and gel content is 89.6%.Result more than shown in the table 1.
Synthesis example 1-6
(1) preparation of liquid
With BA100 part and 0.3 part of mixing of triallyl cyanurate, preparation monomer mixture (IV).
In addition, as the polymerization starter aqueous solution, use the OXI aqueous solution (I) for preparing among the synthesis example 1-1.
(2) manufacturing of acrylic rubber matter polymkeric substance
In the glass reactor processed with whipping appts, raw material and assistant feeding device, thermometer, heating unit etc., pack into 200 parts in water, SSF1.5 part and trisodium phosphate (below be abbreviated as " SPP ".) 0.3 part.Thereafter, on one side under nitrogen gas stream, reaction system is heated on one side in the stirring system.When internal temperature reaches 80 ℃, 30 parts of 100.3 parts of monomer mixtures (IV) and the OXI aqueous solution (I) all are given to reactor through 4 hours continuous supplyings, carry out polymerization.During this time, the internal temperature of reactor remains on 80 ℃.After the interpolation of whole liquids finishes, further made its slaking in 1 hour 80 ℃ of lower maintenances, thereafter, the end polyreaction.The polymerisation conversion of this moment is 97.8%, and the volume average particle size (Mv) of contained acrylic rubber matter polymkeric substance is 87nm in the latex that obtains.In addition, the toluene swell degree is 8, and gel content is 89%.
Then, utilize the method for putting down in writing in the TOHKEMY 2003-138089 communique to carry out the particle diameter hypertrophyization processing that aforesaid propylene acid is rubber polymer.
Add SDSB0.15 part containing to contain in the reactor of latex that aforesaid propylene acid is 100 parts of rubber polymers.Thereafter, on one side the internal temperature of reactor is remained on 25 ℃～30 ℃, on one side under agitation, through adding continuously 60 parts of 5% aqueous acetic acids (particle diameter is loose to be processed) in 30 minutes.Then, after the interpolation of aqueous acetic acid finishes, through adding continuously 20 parts of 10% aqueous sodium hydroxide solutions in 10 minutes.Thus, obtain containing the latex of the acrylic rubber matter polymkeric substance (a1-6) of particle diameter hypertrophyization.The volume average particle size (Mv) of the acrylic rubber matter polymkeric substance in the latex that obtains is 157nm, and size distribution Mv/Mn is 1.15.Result more than shown in the table 1.
Synthesis example 1-7
In the 1st polymerization process, water in the reactor of packing into and the amount of SDBS are respectively outside 200 parts and 2 parts, similarly obtain acrylic rubber matter polymkeric substance (a1-7) with synthesis example 1-1.The volume average particle size (Mv) of the rubber polymer particle in the latex when the 1st polymerization process finishes is 51nm.
Polymerisation conversion when the reaction of the 2nd polymerization process finishes is 99.4%, and the volume average particle size (Mv) of the acrylic rubber matter polymkeric substance (a1-7) in the latex that obtains is 81nm, and size distribution Mv/Mn is 1.04.In addition, the toluene swell degree is 15, and gel content is 90.7%.Result more than shown in the table 1.
Synthesis example 1-8
In the 1st polymerization process, the amount that makes the SDBS in the reactor of packing into is 0.05 part, in the 2nd polymerization process, making in the latex that obtains in the 1st operation the amount with 1/3rd SDBS that pack into of monomer mixture (I) is outside 0.45 part, similarly obtains acrylic rubber matter polymkeric substance (a1-8) with synthesis example 1-1.The volume average particle size (Mv) of the rubber polymer particle in the latex when the 1st polymerization process finishes is 117nm.
Polymerisation conversion when the reaction of the 2nd polymerization process finishes is 98.7%, and the volume average particle size (Mv) of the acrylic rubber matter polymkeric substance (a1-8) in the latex that obtains is 278nm, and size distribution Mv/Mn is 1.04.In addition, the toluene swell degree is 14, and gel content is 91.4%.Result more than shown in the table 1.
Synthesis example 1-9
Replace monomer mixture (I) and use outside the monomer mixture that the AMA by 90 parts BA and 2 parts consists of, similarly obtain acrylic rubber matter polymkeric substance (a1-9) with synthesis example 1-1.The volume average particle size (Mv) of the rubber polymer particle in the latex when the 1st polymerization process finishes is 54nm.
Polymerisation conversion when the reaction of the 2nd polymerization process finishes is 99.3%, and the volume average particle size (Mv) of the acrylic rubber matter polymkeric substance (a1-9) in the latex that obtains is 116nm, and size distribution Mv/Mn is 1.03.In addition, the toluene swell degree is 5, and gel content is 91%.Result more than shown in the table 1.
Synthesis example 1-10
Carry out the 1st polymerization process among the synthesis example 1-1, in reactor, contain under the state of latex, as the 2nd polymerization process, once add 21 parts of the total amount of the monomer mixture that the AMA by 91.7 parts BA and 0.3 part consists of and the OXI aqueous solution (I) shown in the synthesis example 1-1, under 75 ℃, begin polymerization., the internal temperature of reactor remained on 75 ℃, carry out 3 hours polyreaction, obtain acrylic rubber matter polymkeric substance (a1-10) thereafter.
Polymerisation conversion when the reaction of the 2nd polymerization process finishes is 99.2%, and the volume average particle size (Mv) of the acrylic rubber matter polymkeric substance (a1-10) in the latex that obtains is 121nm, and size distribution Mv/Mn is 1.03.In addition, the toluene swell degree is 42, and gel content is 81.9%.Table 1 illustrates above result.
Synthesis example 1-11
Replace monomer mixture (I) and use outside the monomer mixture that the AMA by 91.95 parts BA and 0.05 part consists of, similarly obtain acrylic rubber matter polymkeric substance (a1-11) with synthesis example 1-1.
The volume average particle size (Mv) of the rubber polymer particle in the latex when the 1st polymerization process finishes is 72nm, polymerisation conversion when the reaction of the 2nd polymerization process finishes is 98.3%, the volume average particle size (Mv) of the acrylic rubber matter polymkeric substance (a1-11) in the latex that obtains is 118nm, and size distribution Mv/Mn is 1.03.In addition, the toluene swell degree is 23, and gel content is 64.7%.Table 1 illustrates above result.
[table 1]
Table 1
Figure BDA00002478074600531
2-2. compounded rubber is synthetic
Synthesis example 1-12
With γ-1.96 parts in methacryloxypropyl dimethoxy-methyl silane and 98.04 parts of mixing of organo-siloxane, obtain 100 parts in organo-siloxane mixture.
In 100 parts in this organo-siloxane mixture, be added on 313 parts of solution that are dissolved with 0.68 part of Sodium dodecylbenzene sulfonate in the deionized water, use homogeneous mixer, stirred 5 minutes with 10,000rpm.Thereafter, with 300kg/cm 2Pressure pass into homogenizer 2 times, with organo-siloxane present latex particulate.
Then, in having the removable flask of thermometer, cooling tube and whipping appts, drop into 92 parts of 13 parts of Witco 1298 Soft Acids and deionized waters, the Witco 1298 Soft Acid aqueous solution of preparation 12.4%.Making this aqueous solution is 85 ℃, under agitation, the organo-siloxane latex through dripping by corpusculed obtained above in 8 hours.Temperature 85 ℃ under keep 2 hour after, cooled off thereafter.
, this reactant with aqueous sodium hydroxide solution neutralized, finish polymerization, obtain containing the latex of organopolysiloxane thereafter.The volume average particle size of organopolysiloxane is 60nm.
The latex that obtains was descended dry 30 minutes at 170 ℃, obtain solids component, the result is 18.7%.
Then, in the removable flask with thermometer, nitrogen ingress pipe, cooling tube and whipping appts, drop into by 28.1 parts in the latex (organopolysiloxane is 5.2 parts) that contains organopolysiloxane obtained above.After wherein adding 206 parts of deionized waters, pack into by 0.4 part of polyoxyethylene Sodium Lauryl Sulphate BP/USP, 67.7 parts of n-butyl acrylates, 2.1 parts of allyl methacrylate(AMA)s and 0.28 part of monomer mixed solution that consists of of t-butyl hydroperoxide, stirred 30 minutes, and absorbed by organopolysiloxane rubber.
, to removable flask in pass into nitrogen gas stream carry out nitrogen displacement, reaction system is warming up to 55 ℃ thereafter.When fluid temperature reaches 55 ℃, add making 0.0001 part in ferrous sulfate, 0.0003 part of Calcium Disodium Versenate salt and 0.3 part of aqueous solution that is dissolved in 3.3 parts of deionized waters and forms of rongalite, beginning radical polymerization.By the polymerization of above-mentioned monomer mixed solution, fluid temperature rises to 92 ℃.This state was kept 1 hour, finished the polymerization of monomer, obtain containing the latex of compounded rubber (b1-1).The volume average particle size of the compounded rubber that obtains (b1-1) is 84nm.
2-3. contain rubber reinforced resin synthetic of acrylic rubber matter enhancing by polymer graft resin
The manufacture method of the rubber reinforced resin [S] that has used the acrylic rubber matter polymkeric substance that obtains among above-mentioned synthesis example 1-1～1-11 is shown.
Synthesis example 2-1
(1) preparation of liquid
With vinylbenzene (below be abbreviated as " ST ".) 73 parts, vinyl cyanide (and below be abbreviated as " AN ".) 27 parts and as uncle's lauryl mercaptan of chain-transfer agent (below be abbreviated as " TDM ".) 0.3 part of mixing, preparation monomer mixture (V).
In addition, dissolving EDTA0.05 part, FES0.005 part and NFS0.25 part in 100 parts in water, preparation sulfoxylic acid hydrogen salt be the reductive agent aqueous solution (below be abbreviated as " the SFS aqueous solution (II) ".)。
And, dissolved hydrogen tert-butyl peroxide in 50 parts in water (below be abbreviated as " BHP ".) 0.25 part, the preparation polymerization starter aqueous solution (below be abbreviated as " the CAT aqueous solution (II) ".)。
(2) graft polymerization
In the glass reactor processed with whipping appts, raw material and assistant feeding device, thermometer, heating unit etc., pack into 100 parts in water, 100 parts in acrylic rubber matter polymkeric substance (a1-1), potassium hydroxide (below be abbreviated as " KOH ".) 0.4 part, SDBS3 part and monomer mixture (V) 25% minute.Thereafter, on one side in the stirring system, under nitrogen gas stream, reaction system is heated on one side.When internal temperature reaches 65 ℃, with 50% minute and 30% minute supplied reactor of the CAT aqueous solution (II) of the SFS aqueous solution (II), beginning polymerization.Begin to be warming up to 75 ℃ with 1 hour from polymerization on one side, Yi Bian carry out polyreaction.
After beginning 1 hour from polymerization, when internal temperature reaches 75 ℃, all through the residue of the residue 50% minute of the residue 75% minute of supplying with continuously monomer mixture (V) in 4 hours, the SFS aqueous solution (II) and the CAT aqueous solution (II) 70% minute, proceed polymerization.During this time, the temperature of reaction system remains on 75 ℃.After the interpolation of whole liquids finishes, further after 75 ℃ of lower maintenances made its slaking in 1 hour, finish polyreaction.Thus, obtain containing by acrylic rubber matter enhancing by polymer graft resin and the latex of the rubber reinforced resin (S-1) that consists of of graftomer not.
Then, in this latex, add sal epsom (peptizer), rubber reinforced resin (S-1) is solidified., wash and drying, reclaim rubber reinforced resin (S-1) thereafter.Percentage of grafting shown in the table 2 reaches the not limiting viscosity of graftomer.
Synthesis example 2-2～2-5
In addition the kind of the matter of acrylic rubber shown in the table 2 polymkeric substance and the composition of usage quantity and monomer mixture thereof, similarly obtain rubber reinforced resin (S-2)～(S-5) with synthesis example 2-1.Reaching percentage of grafting not, the limiting viscosity of graftomer is recorded in table 2 simultaneously.
Synthesis example 2-6
(1) preparation of liquid
ST28 part and AN12 part are mixed preparation monomer mixture (VI).
In addition, in 10 parts in water dissolving SPP0.02 part, FES0.004 part and crystalline dextrose (below be abbreviated as " CDX ".) 0.2 part, prepare sugary tetra-sodium and be the reductive agent aqueous solution (below, be abbreviated as " the DX aqueous solution (I) ".)。
(2) graft polymerization
In the glass reactor processed with whipping appts, raw material and assistant feeding device, thermometer, heating unit etc., pack into 240 parts in water, 60 parts in acrylic rubber matter polymkeric substance (a1-6), KOH0.05 part and SSF1.5 part.Thereafter, on one side in the stirring system, under nitrogen gas stream, reaction system is heated on one side.When internal temperature reaches 60 ℃, with the total amount supplied reactor of the DX aqueous solution (I).Thereafter, through 2 hours continuous adding monomer mixtures (VI) and CHP0.25 part, the beginning polymerization.During this time, the temperature with reaction system remains on 60 ℃.The interpolation of whole liquids is warming up to 70 ℃ with internal temperature after finishing, and further after synthermal lower maintenance made its slaking in 1 hour, finishes polyreaction.Thus, obtain containing by acrylic rubber matter enhancing by polymer graft resin and the latex of the rubber reinforced resin (S-6) that consists of of graftomer not.
Then, in this latex, add peptizer, rubber reinforced resin (S-6) is solidified., wash and drying, reclaim rubber reinforced resin (S-6) thereafter.Table 2 illustrates percentage of grafting and reaches the not limiting viscosity of graftomer.
Synthesis example 2-7～2-11
Instead of propylene acid is rubber polymer (a1-1) and use the acrylic rubber matter polymkeric substance (a1-7)～(a1-11) shown in the table 2, substitute monomer mixture and use the monomer mixture of the composition shown in the table 2, in addition, similarly obtain rubber reinforced resin (S-7)～(S-11) with synthesis example 2-1.The percentage of grafting of each resin reaches not, and the limiting viscosity of graftomer is recorded in table 2 simultaneously.
[table 2]
Table 2
Figure BDA00002478074600561
2-4. contain rubber reinforced resin synthetic that compounded rubber strengthens graft resin
The manufacture method of the rubber reinforced resin [T] that has used the compounded rubber (b1-1) that obtains among the above-mentioned synthesis example 2-1 then, is shown.
Synthesis example 2-12
Making the latex that contains 75 parts of the compounded rubbers (b1-1) that obtain among the synthesis example 1-12 is 75 ℃.Thereafter, stir latex, in this latex through 20 minute drip the mixed solution that by BHP0.07 part and MMA12.5 part consisted of and meanwhile, Yi Bian carry out polymerization, dropping is kept this state 30 minutes after finishing.
Then, 75 ℃ under keep reaction system, drip by BHP0.07 part, 9.5 parts of vinylbenzene and 3.0 portions of mixed solutions that consist of of vinyl cyanide through 25 minutes and meanwhile, carry out polymerization on one side.After drip finishing, with reaction system under agitation, under 75 ℃, kept 1 hour, finish polymerization.Thus, obtain containing by compounded rubber and strengthen graft resin and the latex of the rubber reinforced resin (T-1) that consists of of graftomer not.
Then, in this latex, add peptizer, rubber reinforced resin (T-1) is solidified., wash and drying, reclaim rubber reinforced resin (T-1) thereafter.Percentage of grafting is 28%, and the limiting viscosity of graftomer (in the methyl ethyl ketone, 30 ℃) is not 0.35dl/g.
The form of the rubber reinforced resin (T-1) that uses when making composition in addition, is as described below.Namely, on one side above-mentioned latex is used spray drying unit, sprays into the fine droplet shape with the pressure nozzle formula, on one side from supplying with Japanese AEROSIL society hydrophobic silica processed " R-972 " (trade(brand)name) in the mode with respect to the ratio of 100 parts as 0.05 part of rubber reinforced resins (T-1) near the hot-wind inlet, carry out drying (180 ℃ of hot-wind inlet temperature) on one side, obtain the powder that is consisted of by rubber reinforced resin (T-1) and silicon-dioxide.When making composition in the following embodiments, use this powder.
2-5. multipolymer
The polymkeric substance (maleimide based copolymer etc.) that is matched with thermoplastic resin is as described below.
(i) vinylbenzene N-phenylmaleimide acrylonitrile copolymer (U-1)
Used " デ Application カ IP MS-NC " (trade(brand)name) of electrochemical industry society system.Content from the structural unit of N-phenylmaleimide is 44%, and limiting viscosity (in the methyl ethyl ketone, 30 ℃) is 0.26dl/g, and second-order transition temperature is 170 ℃.
(ii) vinylbenzene N-phenylmaleimide acrylonitrile copolymer (U-2)
Used " Port リ イ ミ レ ッ Network ス PAS1460 " (trade(brand)name) of Japanese catalyst society system.Content from the structural unit of N-phenylmaleimide is 40%, and limiting viscosity (in the methyl ethyl ketone, 30 ℃) is 0.27dl/g, and second-order transition temperature is 167 ℃.
(iii) vinylbenzene N-phenylmaleimide acrylonitrile copolymer (U-3)
Used " デ Application カ IP MS-NI " (trade(brand)name) of electrochemical industry society system.Content from the structural unit of N-phenylmaleimide is 50%, and second-order transition temperature is 185 ℃.
(iv) styrene acrylonitrile copolymer (V-1)
Be the polymkeric substance that is obtained by following synthesis example 3-1.
Synthesis example 3-1
(1) preparation of liquid
ST74 part, AN26 part and TDM0.5 part are mixed preparation monomer mixture (VIII).
In addition, dissolving EDTA0.1 part, FES0.005 part and NFS0.2 part in 10 parts in water, the preparation reductive agent aqueous solution (below be abbreviated as " the SFS aqueous solution (IV) ".)。
And, dissolved hydrogen peroxidation diisopropyl benzene in 100 parts in water (below be abbreviated as " IHP ".) 0.25 part, the preparation polymerization starter aqueous solution (below be abbreviated as " the CAT aqueous solution (IV) ".)。
(2) polymerization
In the glass reactor processed with whipping appts, raw material and assistant feeding device, thermometer, heating unit etc., pack into 200 parts in water and SDBS2 part.Thereafter, on one side in the stirring system, under nitrogen gas stream, reaction system is heated on one side.When internal temperature reaches 60 ℃, all through 4 hours the continuous adding monomer mixture (VIII) the total amount of total amount, the SFS aqueous solution (IV) and 80% minute and beginning polymerization of the CAT aqueous solution (IV).The temperature of reaction system is warming up to 70 ℃ when polymerization begins, thereafter, keep synthermal.
Through after 4 hours, the residue of the CAT aqueous solution (IV) was supplied to reactor in 20% minute after the beginning polymerization.And, reaction system after 1 hour, is finished polyreaction 70 ℃ of lower maintenances.Thus, obtain containing the latex of styrene acrylonitrile copolymer (V-1).
, in this latex add sal epsom (peptizer), styrene acrylonitrile copolymer (V-1) is solidified thereafter.Then, wash and drying, reclaim the powder that is consisted of by styrene acrylonitrile copolymer (V-1).Limiting viscosity (in the methyl ethyl ketone, 30 ℃) is 0.42dl/g.
2-6. additive
Use following antioxidant.
(1)F-1
Use octadecyl-3-(3,5-, two-tert-butyl-hydroxy phenyl) propionic ester " ア デ カ ス タ Block AO-50 " (trade(brand)name) of ア デ カ society system.
(2)F-2
Use two (2,6-, two-tertiary butyl-4-aminomethyl phenyl) pentaerythritol diphosphites " ア デ カ ス タ Block PEP-36 " (trade(brand)name) of ア デ カ society system.
3. lampshade thermoplastic resin composition's manufacturing and evaluation
Embodiment 1～8 and comparative example 1～15
Mixing ratio with record in table 3～table 7 drops into raw material [S], [T], [U] and [V] and antioxidant in the Henschel mixer, mixes., use toshiba machine society processed twin screw extruder " TEM-50A " (model name), under 220 ℃～280 ℃ of temperature, carry out melting mixing, obtain pellet thereafter.Use this pellet to carry out the evaluation of above-mentioned projects, its result is recorded in table 3～table 7 simultaneously.In addition, in table 3～table 7, the ratio of the composition of the present invention [A] that record is calculated by material composition, [B], [C] and [D].
[table 3]
Table 3
Annotate: the value the when numerical value of the composition on " thermoplastic resin composition's formation " hurdle is made as 100% for the total with [A], [B], [C] and [D].
[table 4]
Table 4
Figure BDA00002478074600601
Figure BDA00002478074600611
Annotate: the value the when numerical value of the composition on " thermoplastic resin composition's formation " hurdle is made as 100% for the total with [A], [B], [C] and [D].
[table 5]
Table 5
Figure BDA00002478074600612
Figure BDA00002478074600621
Annotate: the value the when numerical value of the composition on " thermoplastic resin composition's formation " hurdle is made as 100% for the total with [A], [B], [C] and [D].
[table 6]
Table 6
Figure BDA00002478074600622
Figure BDA00002478074600631
Annotate: the value the when numerical value of the composition on " thermoplastic resin composition's formation " hurdle is set as 100% for the total with [A], [B], [C] and [D].
[table 7]
Table 7
Figure BDA00002478074600632
Figure BDA00002478074600641
Annotate: the value the when numerical value of the composition on " thermoplastic resin composition's formation " hurdle is made as 100% for the total with [A], [B], [C] and [D].
Learn following situation by the result shown in table 3～table 7.
Comparative example 1 is not for containing the example of composition of the present invention [B], shock resistance and to vibrate deposited property poor.
Comparative example 2 is not for containing the example of composition of the present invention [C], thermotolerance and to vibrate deposited property poor.
Comparative example 3 carries out mixing difficulty with twin screw extruder, in addition, produces in large quantities on the surface of injection-molded article and to think the mixing bad pit that causes (disperseing bad), therefore, does not estimate thereafter.
Comparative example 4 is the poor example of the total of acrylic rubber matter polymkeric substance (a1) and compounded rubber (b1), shock resistance and to vibrate deposited property poor.
Comparative example 5 and comparative example 3 similarly utilize the mixing difficulty of twin screw extruder, in addition, produce in large quantities on the surface of injection-molded article and to think the mixing bad pit that causes (disperseing bad), therefore, do not estimate thereafter.
Comparative example 6 is not for containing the example of composition of the present invention [A], appearance and to vibrate deposited property poor.
Comparative example 7 is for containing the example of the composition that uses the acrylic rubber matter enhancing by polymer graft resin that the little acrylic rubber matter polymkeric substance of volume average particle size obtains, shock resistance and to vibrate deposited property poor.
Comparative example 8 is for containing the example of the composition that uses the acrylic rubber matter enhancing by polymer graft resin that the high acrylic rubber matter polymkeric substance of toluene swell degree obtains, and appearance, the deposited property of vibration and bright property are poor.
Comparative example 9 is for containing the example of the composition that uses the acrylic rubber matter enhancing by polymer graft resin that the large acrylic rubber matter polymkeric substance of volume average particle size obtains, and appearance, the deposited property of vibration and bright property are poor.
Comparative example 10 is for containing the example of the composition that uses the acrylic rubber matter enhancing by polymer graft resin that the large acrylic rubber matter polymkeric substance of size distribution (Mv/Mn) obtains, and appearance, the deposited property of vibration and bright property are poor.
Comparative example 11 is for containing the example of the composition that uses the acrylic rubber matter enhancing by polymer graft resin that the little acrylic rubber matter polymkeric substance of volume average particle size obtains, shock resistance and to vibrate deposited property poor.
Comparative example 12 is for containing the example of the composition that uses the acrylic rubber matter enhancing by polymer graft resin that the large acrylic rubber matter polymkeric substance of volume average particle size obtains, and appearance, the deposited property of vibration and bright property are poor.
Comparative example 13 is for containing the example of the composition that uses the acrylic rubber matter enhancing by polymer graft resin that the low acrylic rubber matter polymkeric substance of toluene swell degree obtains, and shock resistance is poor.
Comparative example 14 is for containing the example of the composition that uses the acrylic rubber matter enhancing by polymer graft resin that the high acrylic rubber matter polymkeric substance of toluene swell degree obtains, and appearance, the deposited property of vibration and bright property are poor.
Comparative example 15 is for containing the example of the composition that uses the acrylic rubber matter enhancing by polymer graft resin that the low acrylic rubber matter polymkeric substance of gel content obtains, and appearance, the deposited property of vibration and bright property are poor.
On the other hand, embodiment 1～8 is the example of composition contained among the present invention, and the balance of shock resistance, thermotolerance, appearance, the deposited property of vibration and bright property is excellent.
Use embodiment 1,2 and 5 composition, carry out the evaluation of the deposited property of hot plate (wire drawing).
To supply with a day smart Resin Industry society electric injection moulding machine processed " エ Le ジ ェ Network ト NEX30 " (trade(brand)name) for the black combination of the evaluation of the appearance of above-mentioned (7), carry out injection molding (220 ℃～260 ℃ of resin temperatures), obtain the tabular test film of 60mm * 30mm * 3mm.
This test film is carried out 3 hours status adjustment under the condition of 23 ℃ of temperature, relative humidity 50%, thereafter, use the deposited trier of hot-plate test sheet (イ ダ makes society of institute system), under the following conditions with test film by being pressed on the hot plate, the wire drawing of visual observation during from hot plate separation test sheet, the result does not produce wire drawing.
＜test conditions＞
Figure BDA00002478074600661
The possibility of industrial application
Lampshade of the present invention is suitable for consisting of the formation of the lampshade of the lamps apparatus for vehicle such as headlight, taillight, stop light with the thermoplastic resin composition.
The explanation of Reference numeral
11: resin lens section (lamp lens)
12: resin cover section (lampshade)

Claims (8)

1. lampshade is used the thermoplastic resin composition, it is characterized in that, contains:
[A] at gel content is more than the 70 quality %, the swelling capacity of toluene is that 5.5～30 times, volume average particle size are that the ratio of 100～200nm and this volume average particle size and number average bead diameter is less than in the presence of 1.1 the acrylic rubber matter polymkeric substance (a1), the acrylic rubber matter enhancing by polymer graft resin that will contain the ethene base system monomer polymerization of aromatic ethenyl compound and vinyl cyanide based compound and obtain
[B] contain organo-siloxane be rubber and have from the compounded rubber (b1) of (being total to) polymer rubber of the structural unit of (methyl) alkyl acrylate in the presence of, the second-order transition temperature that will contain homopolymer surpass 0 ℃ (methyl) acrylic acid alkyl ester compound, aromatic ethenyl compound and vinyl cyanide based compound ethene base system monomer polymerization and the compounded rubber that obtains strengthens graft resin
[C] contains 10～70 quality % from the maleimide based copolymer of the structural unit of maleimide amine compound with respect to the entire infrastructure unit, and
[D] that chooses wantonly contains from from the structural unit of aromatic ethenyl compound, from a kind of structural unit selecting the structural unit of vinyl cyanide based compound and the structural unit from (methyl) acrylic acid alkyl ester compound at least, and do not contain the polymkeric substance from the structural unit of maleimide amine compound;
Be made as in the situation of 100 quality % in the total that with aforesaid propylene acid is rubber polymer enhancing graft resin [A], the enhancing of above-mentioned compounded rubber graft resin [B], above-mentioned maleimide based copolymer [C] and above-mentioned polymkeric substance [D], aforesaid propylene acid be the content of rubber polymer (a1) and above-mentioned compounded rubber (b1) content add up to 8～35 quality %, and
Being made as in the situation of 100 quality % in the total that will to consist of aforesaid propylene acid be the rubber polymer structural unit that strengthens graft resin [A], consist of structural unit that above-mentioned compounded rubber strengthens graft resin [B], consist of the structural unit of above-mentioned maleimide based copolymer [C] and consist of the structural unit of above-mentioned polymkeric substance [D], is 5～30 quality % from the content of the structural unit of maleimide amine compound.
2. lampshade as claimed in claim 1 is used the thermoplastic resin composition, wherein, aforesaid propylene acid is that containing of rubber polymer (a1) and above-mentioned compounded rubber (b1) is proportional, be made as in the total with both in the situation of 100 quality %, be respectively 10～95 quality % and 5～90 quality %.
3. the lampshade described in claim 1 or 2 is used the thermoplastic resin composition, wherein, aforesaid propylene acid is that rubber polymer (a1) is the polymkeric substance that obtains by carrying out successively the 1st polymerization process and the 2nd polymerization process, described the 1st polymerization process is: in the presence of alkylsulfonate and/or alkyl sulfuric ester salt, will by (methyl) acrylic acid alkyl ester compound (m1-1) 50～100 quality % and can with other compounds (m1-2) 0～50 quality % of this (methyl) acrylic acid alkyl ester compound (m1-1) copolymerization (wherein, (m1-1) and (m1-2) add up to 100 quality %.) monomer (m1) that consists of carries out polymerization in aqueous medium, form the operation of the 1st polymkeric substance, described the 2nd polymerization process is: in the presence of above-mentioned the 1st polymkeric substance, in the presence of alkylsulfonate and/or the alkyl sulfuric ester salt or in the presence of non-, will be by (methyl) acrylic acid alkyl ester compound (m2-1) 50～99.99 quality %, have 2 above carbon-to-carbon double bonds polymerizable unsaturated compound (m2-2) 0.01～5 quality % and can with other compounds (m2-3) 0～49.99 quality % of this (methyl) acrylic acid alkyl ester compound (m2-1) and this polymerizable unsaturated compound (m2-2) copolymerization (wherein, (m2-1), (m2-2) and (m2-3) add up to 100 quality %.) monomer (m2) that the consists of operation of in aqueous medium, carrying out polymerization;
The ratio of above-mentioned monomer (m1) and usage quantity (m2) is made as in the total with both in the situation of 100 quality %, is respectively 1～50 quality % and 50～99 quality %.
4. use the thermoplastic resin composition such as each described lampshade in the claim 1～3, it mixes the raw material that comprises following component and obtains:
[S] contain aforesaid propylene acid be rubber polymer (a1) in the presence of, the rubber reinforced resin of the acrylic rubber matter enhancing by polymer graft resin that the ethene base system monomer that does not contain the maleimide amine compound, comprises aromatic ethenyl compound and vinyl cyanide based compound is carried out polymerization and obtain
[T] contains in the presence of above-mentioned compounded rubber (b1), the second-order transition temperature of homopolymer is carried out polymerization above (methyl) acrylic acid alkyl ester compound of 0 ℃, the ethene base system monomer that then will not contain the maleimide amine compound, comprises aromatic ethenyl compound and vinyl cyanide based compound carries out polymerization and the compounded rubber that obtains strengthens the rubber reinforced resin of graft resin, and
[U] contains 10～70 quality % from the maleimide based copolymer of the structural unit of maleimide amine compound with respect to the entire infrastructure unit.
5. use the thermoplastic resin composition such as each described lampshade in the claim 1～4, wherein, above-mentioned lampshade be impregnated in the acetone with the thermoplastic resin composition and the limiting viscosity of the acetone soluble polymer that obtains is 0.2～1.0dl/g.
6. use the thermoplastic resin composition such as each described lampshade in the claim 1～5, it is for forming the molding material of the products formed of evaporation layer on its surface by direct evaporation.
7. use the thermoplastic resin composition such as each described lampshade in the claim 1～6, it is the molding material of the products formed of the deposited method of applicable vibration.
8. products formed is characterized in that, contains in the claim 1～7 each described lampshade and uses the thermoplastic resin composition.
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