CN102918103B - 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
CN102918103B
CN102918103B CN201180026362.2A CN201180026362A CN102918103B CN 102918103 B CN102918103 B CN 102918103B CN 201180026362 A CN201180026362 A CN 201180026362A CN 102918103 B CN102918103 B CN 102918103B
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mentioned
quality
compound
methyl
polymerization
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CN102918103A (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

Thermoplastic resin composition and products formed for lampshade
Technical field
The present invention relates to lampshade with thermoplastic resin composition, the products formed that it gives shock resistance, thermotolerance, molded appearance and deposited property excellence, can obtain with the excellent deposited property of other synthetic resins and after direct evaporation beautiful bright looking.
Background technology
The lamps apparatus for vehicle such as headlight, taillight, stop light generally by resin lens portion (below also referred to as " lamp lens ".) and resin cover portion (below also referred to as " lampshade ".) form.And, as the constituent material of these parts, from the viewpoint of lightweight, productivity etc., resin lens portion has been used the transparent resin such as polymethylmethacrylate (PMMA), polycarbonate (PC), and resin cover portion has been used the resin combination that is combined with tinting material in ABS resin etc.
As the method that engages lamp lens and lampshade, there are the methods such as the deposited method of vibration, the deposited method of hot plate, Laser cladding.Wherein, vibrating deposited method is the vibration that face is exerted pressure and back and forth movement causes that the wish of 2 resin components is engaged, the method of utilizing its heat of friction that the bonding resinous principle melting with position is engaged both, for not needing to heat resin component, can be with the utmost point short period of time by the excellent method engaging between resin component.But in the method, the resin that sometimes produces melting overflows for thread phenomenon is (hereinafter referred to as " wire drawing " in the outside at junction surface.)。When this wire drawing is remarkable, can see from the outside by 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, in order to make wire drawing not obvious, known have make the hiding shape in junction surface method (with reference to patent documentation 1), utilize the refraction of light to make method (with reference to patent documentation 2) that junction surface can not see etc.But any method all specifies the shape of resin component, produce the restriction in design.
On the other hand, vibration as the generation for suppressing wire drawing is deposited with resin combination, the known composition (patent documentation 5) that has the composition (patent documentation 3) of the rubber reinforcement phenylethylene resin series that contains the rubber that has used the special construction taking divinyl rubber as core, the composition (patent documentation 4) that contains the rubber reinforcement phenylethylene resin series that has used the rubber being made up of divinyl and alkyl acrylate, use 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, conventionally by lampshade for secondary processing such as application, metal evaporation, plating.After secondary processing, the beautiful outward appearance forming in order to obtain application, metal evaporation, plating etc., the surface that the surface of the products formed before secondary processing need to be made to smoothness excellence.In order to make the surface smoothing of the products formed of implementing secondary processing, conventionally carry out primary coat processing.When products formed has smoothness, can not form undercoat (below also referred to as " without primary coat ".), directly form metal level etc., can cause the cost of goods.As the formation method of metal level of formation of having omitted undercoat, known have so-called " directly (directly) vapour deposition method ", conventionally used in recent years.Therefore, require not only to suppress wire drawing for the resin combination of the formation of lampshade etc., and give the products formed of smoothness excellence.
On the other hand, as the resin combination that is suitable for direct evaporation, disclose contain by have specific size distribution rubber polymer grafting containing the composition (with reference to patent documentation 6) of rubber graft copolymer.But said composition can not meet the level that requires to high bright property in recent years fully, in addition, about the wire drawing outward appearance at the deposited junction surface of vibration, without any mentioning.
The aesthetic appearance causing as the wire drawing improving in the deposited method of vibration, and for improveing the composition of direct evaporation, the composition (with reference to patent documentation 7) containing rubber graft copolymer that to disclose the rubber mass that contains in rubber, the composition that uses specific gel content be 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 silicon-type rubber reinforced resin.And, in order to give shock resistance, disclose in common acrylic rubber and strengthened the composition (with reference to patent documentation 12) that has used to silicon-type grafting rubbers on a small quantity the multipolymer of alkyl methacrylate in phenylethylene resin series.
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 the 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 thermoplastic resin composition and the products formed that contains it for lampshade, described lampshade gives the products formed of shock resistance, thermotolerance and molded appearance excellence with thermoplastic resin composition, obtain with the excellent deposited property of other synthetic resins and after direct evaporation beautiful bright looking.
For solving the means of problem
The present invention is as described below.
1. lampshade is used thermoplastic resin composition, it contains: [A] is more than 70 quality % at gel content, the swelling capacity of toluene is 5.5～30 times, volume average particle size is 100～200nm, and the ratio of this volume average particle size and number average bead diameter is less than under 1.1 the existence of acrylic rubber matter polymkeric substance (a1), the acrylic rubber matter enhancing by polymer graft resin that the ethene base system monomer that contains aromatic ethenyl compound and vinyl cyanide based compound is carried out to polymerization and obtain, [B] is to contain organo-siloxane be rubber and have under the existence from the compounded rubber (b1) of (being total to) polymer rubber of the structural unit of (methyl) alkyl acrylate, the second-order transition temperature that contains homopolymer is exceeded to (methyl) acrylic acid alkyl ester compound of 0 DEG C, 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 the maleimide based copolymer of 10～70 quality % from the structural unit of maleimide amine compound with respect to 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 containing the polymkeric substance from the structural unit of maleimide amine compound, it is characterized in that, be that rubber polymer strengthens graft resin [A] by 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 is 8～35 quality % that add up to of the content of rubber polymer (a1) and the content of above-mentioned compounded rubber (b1), and be the structural unit that rubber polymer strengthens graft resin [A] forming aforesaid propylene acid, form the structural unit that above-mentioned compounded rubber strengthens graft resin [B], the total that forms the structural unit of above-mentioned maleimide based copolymer [C] and form the structural unit of above-mentioned polymkeric substance [D] is made as in the situation of 100 quality %, content from the structural unit of maleimide amine compound is 5～30 quality %.
2. the lampshade as described in above-mentioned 1 is used thermoplastic resin composition, wherein, aforesaid propylene acid is that containing of rubber polymer (a1) and above-mentioned compounded rubber (b1) is proportional, in the case of both totals are made as 100 quality %, be respectively 10～95 quality % and 5～90 quality %.
3. the lampshade as described in above-mentioned 1 or 2 is used thermoplastic resin composition, wherein, aforesaid propylene acid is that rubber polymer (a1) is the polymkeric substance obtaining by carrying out successively the 1st polymerization process and the 2nd polymerization process, described the 1st polymerization process is under the existence 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 %.) form monomer (m1) in aqueous medium, carry out polymerization, form the operation of the 1st polymkeric substance, described the 2nd polymerization process is under the existence of above-mentioned the 1st polymkeric substance, under the existence of alkylsulfonate and/or alkyl sulfuric ester salt or under non-existence, will be by (methyl) acrylic acid alkyl ester compound (m2-1) 50～99.99 quality %, have more than 2 carbon-to-carbon double bond 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) operation of carrying out polymerization in aqueous medium that forms; The ratio of above-mentioned monomer (m1) and usage quantity (m2), in the case of both totals are made as 100 quality %, is respectively 1～50 quality % and 50～99 quality %.
4. the lampshade as described in any one in above-mentioned 1～3 is with thermoplastic resin composition, it is that the raw material that comprises following component is obtained by mixing: [S] contains in aforesaid propylene acid is under the existence of rubber polymer (a1), to not contain 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 under the existence of above-mentioned compounded rubber (b1), (methyl) acrylic acid alkyl ester compound that the second-order transition temperature of homopolymer is exceeded to 0 DEG C is carried out polymerization, then will not contain 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, [U] contains the maleimide based copolymer of 10～70 quality % from the structural unit of maleimide amine compound with respect to entire infrastructure unit.
5. the lampshade as described in any one in above-mentioned 1～4 is with thermoplastic resin composition, wherein, above-mentioned lampshade be impregnated in acetone with thermoplastic resin composition and the limiting viscosity of the acetone soluble polymer obtaining is 0.2～1.0dl/g.
6. the lampshade as described in any one in above-mentioned 1～5 is with thermoplastic resin composition, and it is for forming the molding material of the products formed of evaporation layer on its surface by direct evaporation.
7. the lampshade as described in any one in above-mentioned 1～6 is with thermoplastic resin composition, and it is for being suitable for the molding material of the products formed that vibrates deposited method.
8. products formed, is characterized in that, contains the lampshade described in any one in above-mentioned 1～7 and uses thermoplastic resin composition.
The effect of invention
Lampshade according to the present invention, with thermoplastic resin composition, can obtain the products formed that shock resistance, thermotolerance, molded appearance and deposited property (especially vibrating deposited) are excellent.And, can obtain with the excellent deposited property of other synthetic resins and after direct evaporation beautiful bright looking.
Brief description of the drawings
Fig. 1 is the general perspective representing for the resin lens portion (lamp lens) of the evaluation of the deposited property of vibration of embodiment.
Fig. 2 is the general perspective representing for the resin cover portion (lampshade) of the evaluation of the deposited property of vibration of embodiment.
Fig. 3 is the resin lens portion (lamp lens) of evaluation of the deposited property of vibration and the summary section of the melt-coating part of resin cover portion (lampshade) representing for embodiment.
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 thermoplastic resin composition, contains: [A] at gel content is more than 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 that the ratio of 100～200nm and this volume average particle size and number average bead diameter is less than under 1.1 the existence of acrylic rubber matter polymkeric substance (a1), by the ethene base system monomer that contains aromatic ethenyl compound and vinyl cyanide based compound (below 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 also referred to as " composition [A] ".), [B] to contain organo-siloxane be rubber and have under the existence from the compounded rubber (b1) of (being total to) polymer rubber of the structural unit of (methyl) alkyl acrylate, and the ethene base system monomer that the second-order transition temperature that contains homopolymer is exceeded to (methyl) acrylic acid alkyl ester compound, aromatic ethenyl compound and the vinyl cyanide based compound of 0 DEG C carries out polymerization and the compounded rubber that obtains strengthens graft resin (below also referred to as " composition [B] ".), [C] with respect to entire infrastructure unit contain 10～70 quality % from the maleimide based copolymer of the structural unit of maleimide amine compound (below also referred to as " composition [C] ".), [D] as required contains and is selected from from the structural unit of 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 containing the polymkeric substance of the structural unit from maleimide amine compound (below also referred to as " composition [D] ".), by 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 is 8～35 quality % that add up to of the content of rubber polymer (a1) and the content of above-mentioned compounded rubber (b1), and at the structural unit that will form mentioned component [A], form the structural unit of mentioned component [B], the total that forms the structural unit of mentioned component [C] and the structural unit of formation mentioned component [D] is made as in the situation of 100 quality %, content from the structural unit of maleimide amine compound is 5～30 quality %.
Mentioned component [A] is for by being, under the existence of rubber polymer (a1), ethene base system monomer (a2) is carried out to polymerization (hereinafter referred to as " graft polymerization " in aforesaid propylene acid.) 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 portion and the multipolymer portion formation comprising from the structural unit of ethene base system monomer (a2).
In addition, the rubber reinforced resin obtaining by graft polymerization strengthens graft resin except rubber polymer conventionally, 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, in the situation that above-mentioned ethene base system monomer (a2) contains maleimide amine compound, the not graftomer obtaining is included in composition [C] conventionally in composition of the present invention.In addition, in the situation that above-mentioned ethene base system monomer (a2) contains other aromatic ethenyl compounds except maleimide amine compound and vinyl cyanide based compound and/or (methyl) acrylic acid alkyl ester compound, the not graftomer obtaining is included in composition [D] conventionally in composition of the present invention.
Aforesaid propylene acid is that rubber polymer (a1) is that gel content is that 70 quality % are above, toluene swell degree is that 5.5～30 times, volume average particle size are the polymkeric substance (acrylic rubber) that the ratio of 100～200nm and volume average particle size and number average bead diameter is less than 1.1.And this acrylic rubber matter polymkeric substance (a1) is generally has that to contain from the polymkeric substance portion of the structural unit of (methyl) acrylic acid alkyl ester compound, at 25 DEG C be (being total to) polymkeric substance of rubber mass.
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, can be also the multipolymer that contains this structural unit.This multipolymer can be for containing two or more 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, it can be also non-cross-linked polymer.
As formation aforesaid propylene, acid is rubber polymer (a1), for (methyl) acrylic acid alkyl ester compound of the formation from 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 two or more.In addition, wherein, the compound that preferably carbonatoms of the alkyl of ester portion is 1～14, particularly preferably n-butyl acrylate and 2-EHA.
In addition, aforesaid propylene acid is that rubber polymer (a1) is in the situation of multipolymer, be used for the compound (ethene base system monomer) of the formation of other structural units, except (methyl) acrylic acid alkyl ester compound, it can be the compound that there is the compound of 1 carbon-to-carbon double bond and/or there is more than 2 carbon-to-carbon double bond.
As the compound with 1 carbon-to-carbon double bond, can enumerate: aromatic ethenyl compound, vinyl cyanide based compound, containing 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, 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.
, can enumerate: acrylamide, Methacrylamide etc. containing amido unsaturated compound as above-mentioned.
As abovementioned alkyl vinyl ether, the compound that the carbonatoms that can enumerate the alkyl that forms alkyl portion is 1～6.
In addition, as the compound with more than 2 carbon-to-carbon double bond, 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.
As aforesaid propylene, acid is rubber polymer (a1), preferably contains the multipolymer from the structural unit of (methyl) acrylic acid alkyl ester compound.In this case, when the total amount of whole structural unit of formation multipolymer is made as to 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 are irrelevant, is more than 70 quality %, more than being preferably 75 quality %, more preferably more than 80 quality %.While using the high acrylic rubber matter polymkeric substance (a1) of gel content, be equipped with metal level etc. on the surface of the products formed that obtains, can obtain excellent bright property.
In addition, aforesaid propylene acid is that the toluene swell degree of rubber polymer (a1) and the kind of structural unit are irrelevant, is 5.5～30 times, is preferably 6～25 times, more preferably 10～23 times.While using the acrylic rubber matter polymkeric substance (a1) of above-mentioned scope, can obtain the products formed of shock resistance excellence, be equipped with metal level etc. on the surface of the products formed that obtains, can obtain excellent bright property.
In addition, above-mentioned gel content and toluene swell degree can utilize for example following method to obtain.
First, approximately 0.2 gram of weighing acrylic rubber matter polymkeric substance (a1) (is designated as Wr by quality.), drop in toluene 25ml, stir lightly., 25 DEG C at place 48 hour, use the 200 object wire nettings that weigh in advance (quality to be designated as to Wm gram thereafter.) filter, be separated into insoluble point and solvable point.After separation, weigh (quality is designated as to W1 gram) by insoluble point with together with the wire netting of filtering separation rapidly, deduct the weighing value (Wm) of wire netting from this weighing value (W1), obtain (quality being designated as to Ws gram by the weighing value of insoluble point of toluene swell.)。Secondly, owing to containing toluene with in insoluble point of toluene swell, therefore, by its at 25 DEG C air-dry 12 hours, then use Vacuumdrier at 60 DEG C dry 12 hours, thus toluene contained in insoluble point is dried and is removed.Dried insoluble point is weighed and (quality be designated as to W2 gram together with wire netting.), deducting the weighing value (Wm) of wire netting from this weighing value (W2), the dry weight that obtains insoluble point (is designated as Wd gram by 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 using when in addition, above-mentioned gel content and toluene swell degree are manufactured acrylic rubber matter polymkeric substance (a1) by being suitably 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 is that the volume average particle size of rubber polymer (a1) is (below also referred to as " Mv ".) be 100～200nm, be preferably 105～180nm, more preferably 110～170nm.
In addition, by the volume average particle size (Mv) of above-mentioned acrylic rubber matter polymkeric substance (a1) and number average bead diameter (below also referred to as " Mn ".) the size distribution (Mv/Mn) that represents of ratio be less than 1.1, be preferably less than 1.07.
In above-mentioned Mv and/or size distribution (Mv/Mn), in above-mentioned extraneous situation, the shock resistance of products formed, bright property and the inhibition of vibrating the wire drawing when deposited sometimes becomes insufficient.
Aforesaid propylene acid is that Mv and the Mn of rubber polymer (a1) can utilize for example 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
Alkylsulfonate and/or alkyl sulfuric ester salt (below by them 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 forms carries out polymerization in aqueous medium, forms the polymerization process of the 1st polymkeric substance.
(2) the 2nd polymerization process
Under the existence of above-mentioned the 1st polymkeric substance, under the existence of alkylsulfonate and/or alkyl sulfuric ester salt (emulsifying agent (e)) or under non-existence, will be by (methyl) acrylic acid alkyl ester compound (m2-1) 50～99.99 quality %, have more than 2 carbon-to-carbon double bond 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 %.) form monomer (m2) in aqueous medium, carry out polymerization, obtain the operation of multipolymer (a11).
And, with regard to the ratio of the monomer (m1) that uses in above-mentioned polymerization process and usage quantity (m2), in the case of both totals are made as 100 quality %, be respectively 1～50 quality % and 50～99 quality %.
Above-mentioned the 1st polymerization process be under the existence 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 forms carries out letex polymerization in aqueous medium, forms the operation of the 1st polymkeric substance.In the time of 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 compound that the carbonatoms that preferably uses the alkyl of ester portion is 1～14, 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 two or more.
In addition, as above-mentioned can with other compounds (m1-2) of (methyl) acrylic acid alkyl ester compound (m1-1) copolymerization, conventionally 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), in the case of both totals being made as 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 excellence, the generation of wire drawing when inhibition vibration is deposited.
In addition, in above-mentioned the 1st polymerization process, in reaction system, make emulsifying agent (e) exist, carry out the polymerization of monomer.By using mentioned emulsifier (e), can manufacture efficiently for making gel content be that 70 quality % are above, the swelling capacity of toluene is that 5.5～30 times, volume average particle size are the 1st polymkeric substance that the ratio of 100～200nm and volume average particle size and number average bead diameter is less than 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.
The compound that above-mentioned sulfonated alkane can use following general formula (1) to represent.
R 1-SO 3M (1)
(in formula, R 1for the alkyl of carbonatoms 8～20, M is Na or K.)
The compound that abovementioned alkyl benzene sulfonate can use following general formula (2) to represent.
[changing 1]
(in formula, R 2for the alkyl of carbonatoms 10～18, M is Na or K.)
In addition, abovementioned alkyl naphthalenesulfonate can use the compound that following general formula (3) represents.
[changing 2]
(in formula, R 3for 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, particularly preferably Sodium dodecylbenzene sulfonate.
As 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 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 to 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 in the time of above-mentioned scope, can manufacture efficiently the 1st polymkeric substance for making the acrylic rubber matter polymkeric substance (a1) with above-mentioned character, in addition, can make the products formed obtaining become the products formed of shock resistance and bright property excellence.
In addition, and in situation with above-mentioned alkylsulfonate and alkyl sulfuric ester salt, in the case of both totals being made as 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 %.
As the using method of the emulsifying agent (e) in above-mentioned the 1st polymerization process, can be: the method that total amount is once packed into reaction system before polymerization; A part is made an addition in reaction system to the method for after polymerization starts, its remainder separately or continuously being added before polymerization; The method of separately or continuously adding after polymerization starts 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-tertiary hexyl superoxide, tert-pentyl-tertiary hexyl superoxide, two (tertiary hexyl) superoxide, Cyclohexanone peroxides, 3,3,5-trimethyl hexanone peroxide, methyl cyclohexanone peroxide, two (t-butyl peroxy)-3,3 of 1,1-, 5-trimethyl-cyclohexane, two (t-butyl peroxy) hexanaphthenes of 1,1-, normal-butyl-4, two (t-butyl peroxy) valerates of 4-, Cumene Hydroperoxide 80, 2,5-dimethylhexane-2,5-dihydro-peroxidase, two (the t-butyl peroxy)-sec.-propyl of 1,3-) benzene, 2,5-dimethyl-2,5-bis-(t-butyl peroxy) hexane, diisopropyl benzene superoxide, tert-butyl peroxide cumyl, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, peroxidation 2,4 dichloro benzene formyl, the peroxidation lauric acid tert-butyl ester, the peroxidation list carbonic acid tert-butyl ester, two (tert-butylcyclohexyl) peroxy dicarbonate, peroxidized t-butyl perbenzoate, 2,5-dimethyl-2,5-bis-(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-dicyanopropanes, 2,2 '-azo two (2,4,4-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 oxidation-reduction type polymerization starter, can use taking S-WAT, Sulfothiorine, rongalite, xitix, ferrous sulfate etc. as reductive agent the oxidation-reduction type polymerization starter taking potassium persulphate, hydrogen peroxide, t-butyl hydroperoxide etc. as oxygenant.
As above-mentioned polymerization starter, preferably inorganic peroxide.
In the situation that above-mentioned monomer (m1) is made as to 100 mass parts, the usage quantity of above-mentioned polymerization starter is preferably 0.01～3.0 mass parts, more preferably 0.03～2.0 mass parts, 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 in the time of above-mentioned scope, can manufacture efficiently the 1st polymkeric substance for making the acrylic rubber matter polymkeric substance (a1) with above-mentioned character, in addition, can make the products formed obtaining become the products formed of shock resistance and bright property excellence.
As the using method of the polymerization starter in above-mentioned the 1st polymerization process, can be: the method that total amount is once packed into reaction system before polymerization; Before polymerization, a part is made an addition to reaction system, the method for after polymerization starts, its remainder separately or continuously being added etc.
In above-mentioned the 1st polymerization process, use in the situation of chain-transfer agent (molecular weight regulator), can use the halogenated hydrocarbon such as chloroform, carbon tetrabromide; The thio-alcohols such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tertiary lauryl mercaptan, Thiovanic acid; The xanthan acids such as dimethyl yellow ortho acid disulphide, di-isopropyl xanthogenic acid disulphide; The current known compound such as terpinolene, α-methylstyrenedimer.In above-mentioned chain-transfer agent, preferred tertiary lauryl mercaptan.
In the situation that above-mentioned monomer (m1) is made as to 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 is too much, the shock resistance of products formed becomes insufficient sometimes.
As the using method of the chain-transfer agent in above-mentioned the 1st polymerization process, can be: the method that total amount is once packed into reaction system before polymerization; Before polymerization, a part is made an addition to reaction system, the method for after polymerization starts, its remainder separately or continuously being added etc.
In above-mentioned the 1st polymerization process, use in electrolytical situation, can use the current known compounds such as potassium sulfate, salt of wormwood, sodium carbonate, potassium hydroxide, sodium bicarbonate, trisodium phosphate, potassiumphosphate, V-Brite B.These compounds may be used singly or in combination of two or more.In above-claimed cpd, preferably salt of wormwood, sodium carbonate, sodium bicarbonate and V-Brite B.
In the situation that above-mentioned monomer (m1) is made as to 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, in the time of above-mentioned scope, can be manufactured the 1st polymkeric substance of the multipolymer (a11) for being made as the acrylic rubber matter polymkeric substance (a1) with above-mentioned character efficiently.
As the electrolytical using method in above-mentioned the 1st polymerization process, can be: the method that total amount is once packed into reaction system before polymerization; Before polymerization, a part is made an addition to reaction system, the method for after polymerization starts, its remainder separately or continuously being added; The method of separately or continuously adding after polymerization starts etc.
Polymerization temperature in above-mentioned the 1st polymerization process is generally 65 DEG C～98 DEG C, is preferably 70 DEG C～95 DEG C.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.By the pH of reaction system is maintained to above-mentioned scope, carry out polymerization simultaneously, can manufacture efficiently the 1st polymkeric substance of the multipolymer (a11) for being made as the acrylic rubber matter polymkeric substance (a1) with above-mentioned character.
Above-mentioned the 1st polymerization process is preferably more than 85%, more preferably more than 90%, particularly preferably more than 95% moment finishes at polymerisation conversion.The in the situation that of end, even if sometimes use the 1st polymkeric substance obtaining to supply with the 2nd polymerization process, can not obtain having the acrylic rubber matter polymkeric substance (a1) of above-mentioned character in the time that above-mentioned polymerisation conversion is low.
In addition, the in the situation that of more than 85% finishing above-mentioned the 1st polymerization process at polymerisation conversion, the volume average particle size of the 1st polymkeric substance obtaining is generally 40～120nm.
Above-mentioned the 2nd polymerization process is under the existence of above-mentioned the 1st polymkeric substance, under the existence of alkylsulfonate and/or alkyl sulfuric ester salt (emulsifying agent (e)) or under non-existence, will be by (methyl) acrylic acid alkyl ester compound (m2-1) 50～99.99 quality %, have more than 2 carbon-to-carbon double bond 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 %.) form monomer (m2) in aqueous medium, carry out polymerization, 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 in different reaction systems, carry out.Carrying out, can under the existence of emulsifying agent (e), carry out polymerization in different reaction systems, also can under the non-existence of emulsifying agent (e), carry out.In the latter's situation, can use other emulsifying agents.
The in the situation that of using 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 forms above-mentioned monomer (m2), the compound that the carbonatoms that preferably uses the alkyl of ester portion is 1～14, 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 two or more.
As the above-mentioned polymerizable unsaturated compound (m2-2) with more than 2 carbon-to-carbon double bond, preferably use (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., particularly preferably use allyl methacrylate(AMA) and triallyl cyanurate.In addition, above-mentioned polymerizable unsaturated compound (m2-2) can use separately, also can use two or more.
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, conventionally 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 (m2-1), polymerizable unsaturated compound (m2-2) and other compounds (m2-3) that use in above-mentioned the 2nd polymerization process, in the case of their total being made as 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 excellence, the generation of wire drawing when 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, in the case of both totals being set as 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 excellence, the generation of wire drawing when inhibition vibration is deposited.
Above-mentioned the 2nd polymerization process is by the operation of above-mentioned monomer (m2) polymerization under the existence of the 1st polymkeric substance that obtains in above-mentioned the 1st polymerization process, the total amount of monomer (m2) once can be made an addition to reaction system and carries out polymerization, also can separate or add continuously monomer (m2) on one side, carry out polymerization on one side.About the using method of emulsifying agent, polymerization starter, chain-transfer agent (molecular weight regulator) etc., can be same with the method in above-mentioned the 1st polymerization process.
As mentioned above, above-mentioned the 2nd polymerization process can carry out in the reaction system identical with the 1st polymerization process, also can in different reaction systems, carry out.
In the reaction system identical with the 1st polymerization process, carry out above-mentioned the 2nd polymerization process, in the latex that contains the 1st polymkeric substance obtaining, add above-mentioned monomer (m2) and carry out polymerization in the 1st polymerization process, also can again add as required aqueous medium etc.
In addition, in new reaction system, carry out, above-mentioned the 2nd polymerization process, can be used as it is the latex that contains the 1st polymkeric substance obtaining in above-mentioned the 1st polymerization process, also can use as required the suspension that makes this latex suspend in aqueous medium.
Under the existence of mentioned emulsifier (e), carry out above-mentioned the 2nd polymerization process, the preferred combination of preferred kind, alkylsulfonate and the alkyl sulfuric ester salt of emulsifying agent (e) and the using method of emulsifying agent (e) are same with those in above-mentioned the 1st polymerization process.
In addition, in the situation that above-mentioned monomer (m2) is made as to 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 in the time of above-mentioned scope, can manufacture efficiently as the multipolymer (a11) of acrylic rubber matter polymkeric substance (a1) with above-mentioned character, in addition, the products formed obtaining can be made to the products formed of shock resistance and bright property excellence.
And, the in the situation that of using polymerization starter, chain-transfer agent (molecular weight regulator), ionogen etc. in above-mentioned the 2nd polymerization process, preferably use compound and the using method identical with the situation that uses 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 DEG C～98 DEG C, is preferably 70 DEG C～95 DEG C.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 one side the pH of reaction system being maintained to above-mentioned scope, can manufacture efficiently as the multipolymer (a11) of acrylic rubber matter polymkeric substance (a1) with above-mentioned character.
Above-mentioned the 2nd polymerization process is preferably more than 85%, more preferably more than 90%, particularly preferably more than 95% moment finishes at polymerisation conversion.The in the situation that of more than 85% finishing above-mentioned the 2nd polymerization process at polymerisation conversion, can manufacture efficiently as the multipolymer (a11) of acrylic rubber matter polymkeric substance (a1) with above-mentioned character.In addition, when reducing above-mentioned polymerisation conversion and finishing polymerization, the particle diameter of the acrylic rubber matter polymkeric substance sometimes obtaining is little, and it is insufficient that shock resistance becomes.
As aforesaid propylene, acid is rubber polymer (a1), headed by the multipolymer (a11) that can use to obtain as described above, make to utilize at present the acrylic rubber matter polymkeric substance hypertrophyization that known method obtains and the polymkeric substance obtaining.
As the method for hypertrophy processing, can be set forth in the method for adding the acid such as acetic anhydride, acetic acid, nitric acid, phosphoric acid in the latex that contains hypertrophyization polymkeric substance.Wherein, preferably acetic anhydride, thus, can make and on the particle diameter after hypertrophy, not have acrylic rubber matter polymkeric substance devious (a1).
As aforesaid propylene, acid is rubber polymer (a1), can use any that there is no the polymkeric substance of hypertrophyization and the polymkeric substance of hypertrophyization, also they can be used in combination.
In aforesaid propylene acid be under the existence of rubber polymer (a1) for the ethene base system monomer (a2) of polymerization the monomer for containing aromatic ethenyl compound and vinyl cyanide based compound, can contain as required (methyl) acrylic compound, maleimide amine compound, unsaturated acid anhydride, containing carboxyl unsaturated compound, hydroxyl unsaturated compound, containing amino unsaturated compound, containing amido unsaturated compound, containing epoxy group(ing) unsaturated compound, contain azoles quinoline base unsaturated compound etc.In addition, the ratio of the aromatic ethenyl compound in 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 thering is 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 two or more.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 two or more.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 two or more.
As above-mentioned maleimide amine compound, can enumerate: maleimide, N-methyl maleimide, N-sec.-propyl maleimide, N-butyl maleimide, N-dodecyl maleimide, N-phenylmaleimide, N-(2-aminomethyl phenyl) maleimide, N-(4-aminomethyl phenyl) maleimide, N-(2, 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 two or more.In addition, as import the additive method from the structural unit of maleimide amine compound in mentioned component [A], can, for for example the unsaturated dicarboxylic acid acid anhydride of maleic anhydride is carried out to 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 two or more.
, can enumerate: (methyl) vinylformic acid, ethylacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid, β-crotonic acid, styracin etc. containing carboxyl unsaturated compound as above-mentioned.These compounds can be used singly or in combination two or more.
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, 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 two or more.
, can enumerate: (methyl) acrylic-amino ethyl ester containing amino unsaturated compound as above-mentioned, (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 amino) ethyl ester, (methyl) vinylformic acid 2-dimethylamino propyl ester, (methyl) vinylformic acid 2-diethylamino propyl ester, (methyl) vinylformic acid 2-(two-n-propyl amino) propyl ester, (methyl) vinylformic acid 3-dimethylamino propyl ester, (methyl) vinylformic acid 3-diethylamino propyl ester, (methyl) vinylformic acid 3-(two-n-propyl 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 two or more.
, can enumerate: (methyl) acrylamide, N-methylol (methyl) acrylamide, 3-dimethylaminopropyl (methyl) acrylamide etc. containing amido unsaturated compound as above-mentioned.These compounds can be used singly or in combination two or more.
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 two or more.
Contain as above-mentioned azoles quinoline base unsaturated compound, can enumerate vinyl azoles quinoline etc.
As mentioned component [A], preferred graft resin is as described below.
(1), under the existence of acrylic rubber matter polymkeric substance (a1), the ethene base system monomer (a2-1) being made up of is carried out to polymerization and the resin that obtains aromatic ethenyl compound and vinyl cyanide based compound;
(2) under the existence of acrylic rubber matter polymkeric substance (a1), by the resin that carries out polymerization by the ethene base system monomer (a2-2) of aromatic ethenyl compound, vinyl cyanide based compound and (methyl) acrylic compound formation and obtain.
As mentioned above, mentioned component [A] is by acrylic rubber matter polymkeric substance portion and the multipolymer portion formation containing from the structural unit of ethene base system monomer (a2).From the shock resistance of products formed and the viewpoint of bright property, with respect to total 100 mass parts of acrylic rubber matter polymkeric substance portion and multipolymer portion, the content that forms the acrylic rubber matter polymkeric substance portion 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 portion 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 portion is very few, shock resistance is insufficient sometimes.
The method of manufacturing mentioned component [A] is not particularly limited, and can be suitable for known method.As the method for graft polymerization, can be letex polymerization, suspension polymerization, solution polymerization, mass polymerization or the polymerization by these Combination of Methods.Wherein, preferred emulsion polymerization.In addition, in above-mentioned polymerization, except composition [A], by-product is graftomer not.
Manufacture in the situation of mentioned component [A], the usage quantity of acrylic rubber matter polymkeric substance (a1) and ethene base system monomer (a2), from the viewpoint of shock resistance and bright property, in the case of both total amounts being made as 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, in the time manufacturing mentioned component [A], can in reaction system, add ethene base system monomer (a2) next time and start polymerization in the existence of acrylic rubber matter polymkeric substance (a1) total amount, also can separate or continuously add while carry out polymerization.In addition, can exist lower or non-existence add ethene base system monomer (a2) next time and start polymerization in the part of acrylic rubber matter polymkeric substance (a1), also can separate or interpolation continuously.Now, can reaction midway once, separately or add continuously the remainder that aforesaid propylene acid is rubber polymer (a1).
In the situation that carrying 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 reaction system.
As above-mentioned chain-transfer agent, preferably thio-alcohol, particularly preferably tertiary 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 5 quality %.
In addition, above-mentioned chain-transfer agent can once or continuously make an addition in 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: alkyl ester type compound, the alkyl ether type compound etc. of polyoxyethylene glycol.These materials can use separately a kind or be used in combination two or more.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 to polymerization is generally 40 DEG C～80 DEG C, is preferably 50 DEG C～75 DEG C.In addition, polymerization time is generally 4～8 hours.
The pH of the reaction system in letex polymerization is not particularly limited, and is generally 8～12 scope, is preferably 9～12.Carry out polymerization on one side by the pH of reaction system being maintained to above-mentioned scope on one side, can carry out efficiently the formation of composition [A].
Letex polymerization is preferably more than 85%, more preferably more than 90%, particularly preferably more than 95% moment finishes at polymerisation conversion.The in the situation that of more than 85% finishing this letex polymerization at polymerisation conversion, can use the composition that contains the composition [A] obtaining to obtain the products formed of shock resistance and bright property excellence.
After letex polymerization finishes, the latex that contains composition [A] is utilized conventionally to the solidifying of resinous principle of peptizer, make powder etc.,, wait by washing and refine, be dried and reclaim thereafter.In the time solidifying, can use current known peptizer, can use the inorganic salt such as calcium chloride, magnesium sulfate, magnesium chloride, calcium acetate; The mineral acid such as sulfuric acid, hydrochloric acid; The organic acid such as acetic acid, lactic acid etc.
Manufacture by solution polymerization, mass polymerization and body-suspension polymerization in the situation of composition [A], can be suitable for known method.
Because the rubber reinforced resin obtaining as described above contains composition [A] and graftomer not conventionally, therefore, by in composition [A] and 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, at 25 DEG C, carry out the stirring etc. of 2～6 hours, insoluble point of generating and solvable point (acetone soluble polymer) are separated, reclaimed.
Acetone soluble polymer is equivalent to not graftomer, as mentioned above, according to the kind of the ethene base system monomer (a2) using, has the material being included in composition [C] and/or composition [D].
From the viewpoint of forming process, shock resistance, bright property etc., percentage of grafting in mentioned component [A], be preferably 5～200 quality % in containing from the ratio of the multipolymer of the structural unit of ethene base system monomer (a2) of the upper grafting of acrylic rubber matter polymkeric substance (a1), more preferably 10～150 quality %, more preferably 20～120 quality %.When percentage of grafting is too low, the shock resistance of products formed is insufficient sometimes.On the other hand, when percentage of grafting is too high, forming process is insufficient sometimes.
Above-mentioned percentage of grafting can utilize following formula to obtain.
Percentage of grafting (%)={ (S-T)/T} × 100
In formula, S drops into the rubber reinforced resin obtaining by graft polymerization in acetone, use after bobbing machine vibration (temperature 23 DEG C, 2 hours), use separating centrifuge to carry out centrifugation (0 DEG C of temperature, revolution 28,000rpm, 1 hour), by the quality (g) of insoluble point and solvable point of insoluble point of being isolated (temperature 60 C, 12 hours dry), T is the quality (g) of acrylic rubber matter polymkeric substance (a1) contained in 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 by for example suitably selecting the supply method of the kind of the kind of the polymerization starter using when the manufacture 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. to adjust.
Mentioned component [B] is for to contain organo-siloxane be rubber and have under the existence from the compounded rubber (b1) of (being total to) polymer rubber of the structural unit of (methyl) alkyl acrylate, and the ethene base system monomer that the second-order transition temperature that contains homopolymer is exceeded to (methyl) acrylic acid alkyl ester compound, aromatic ethenyl compound and the vinyl cyanide based compound of 0 DEG C is (below 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 portion with contain the resin forming from the multipolymer portion of the structural unit of ethene base system monomer (b2).
Being to be that rubber and having from (be total to) polymer rubber of the structural unit of (methyl) alkyl acrylate forms by organo-siloxane for the compounded rubber (b1) of the formation of mentioned component [B], is that both such as pass through to be wound around 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 containing from the structural unit of (methyl) alkyl acrylate, preferably poly-(methyl) acrylate (b1-2) described later.
As the compounded rubber (b1) that contains above-mentioned organopolysiloxane (b1-1) and poly-(methyl) acrylate (b1-2), can use and utilize under the existence 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 under the existence of poly-(methyl) acrylate (b1-2), organo-siloxane is carried out to 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 preferably cyclic organic siloxane links via grafting intersection agent, preferably intersects agent (hereinafter referred to as " agent of siloxanes intersection " by the cyclic organic siloxane and the organopolysiloxane grafting that contain more than 3 rings.) organo-siloxane mixture carry out letex polymerization and the material that obtains.Organo-siloxane mixture can contain linking agent for organopolysiloxane as required (hereinafter referred to as " siloxane crosslinker ".)。
As cyclic organic siloxanes more than above-mentioned 3 rings, the preferably compound of 3～6 rings.As cyclic organic siloxane, can enumerate: hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane, ten diformazan basic ring 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 there is the alkoxysilane compound containing trialkylsilyl group in molecular structure of vinyl.
As above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure, can enumerate: the methacryloxypropyl silanes such as 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, δ-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 there is 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 preferably tetraalkoxysilane, particularly preferably tetraethoxysilane.
In the situation that above-mentioned organo-siloxane mixture is made up of cyclic organic siloxane, siloxanes intersection agent and siloxane crosslinker, the ratio of the usage quantity of these compositions, in the case of their total is made as 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 organo-siloxane mixture, add emulsifying agent and water and obtain latex, carrying out after the corpusculed of latex, itself and acid catalyst are mixed and make to the method for its reaction.
(2) in organo-siloxane mixture, add acid catalyst with emulsifying agent together with water and make latex, 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, more than the usage quantity of mentioned emulsifier is preferably 0.05 mass parts.In addition, painted, the thermoplastic resin composition's who himself causes for fear of emulsifying agent the deteriorated painted impact causing, 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 aforesaid method (1), preferably use the acid catalyst aqueous solution that is dissolved in water and form.Preferably by the acid catalyst aqueous solution by after heating and becoming high temperature, 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 obtaining, preferably.
In addition, in aforesaid method (2), can directly use acid catalyst, also can use the acid catalyst aqueous solution that is dissolved in water and form.And, acid catalyst or the acid catalyst aqueous solution can be made an addition in organo-siloxane mixture, emulsifying agent and water and mix.
In the time of the letex polymerization of above-mentioned organo-siloxane mixture, as the device that latex is carried out to corpusculed, can enumerate the shearing force that the high speed rotating of the lyophobic dust in latex is formed and make atomic homogeneous mixer, make atomic homogenizer etc. by 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, 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 preferably about 1 hour.On the other hand, in aforesaid method (2), polymerization time is preferably more than 2 hours, more preferably more than 5 hours.
In addition, polymerization temperature is all preferably more than 50 DEG C in any situation, more preferably more than 80 DEG C.
Stopping of letex polymerization can be by cooling by reaction solution, further with in the alkaline matters such as sodium hydroxide, potassium hydroxide, sodium carbonate and carry out.
The volume average particle size of the organopolysiloxane (b1-1) obtaining by above operation is preferably below 120nm, more preferably below 100nm.Wherein, lower limit is generally 60nm.
Thereafter, by the monomer that contains (methyl) acrylic acid alkyl ester compound (mm) being carried out to polymerization under the existence of the organopolysiloxane obtaining (b1-1), can obtain the compounded rubber (b1) that contains organopolysiloxane (b1-1) and poly-(methyl) acrylate (b1-2).
Above-mentioned monomer (mm) can be only (methyl) acrylic acid alkyl ester compound, also can be made up of (methyl) acrylic acid alkyl ester compound and other compounds.
Above-mentioned (methyl) acrylic acid alkyl ester compound is preferably the compound that the carbonatoms of the alkyl of ester portion is 1～14.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 two or more.
As above-mentioned (methyl) acrylic acid alkyl ester compound, preferably 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, as 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 have 1 carbon-to-carbon double bond compound, there is compound of more than 2 carbon-to-carbon double bond etc.
As other compounds, preferably there is the compound of more than 2 carbon-to-carbon double bond, preferably use poly-(methyl) acrylate to intersect agent (hereinafter referred to as " agent of acrylic acid series intersection " with grafting.) and gather (methyl) linking agent for acrylate (hereinafter referred to as " acrylic acid series linking agent ".)。
The intersection agent of aforesaid propylene acid system is preferably compounds different from the reactivity of (methyl) acrylic compound in multiple carbon-to-carbon double bonds contained in molecule.
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).
As aforesaid propylene, acid is linking agent, 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 up of (methyl) acrylic acid alkyl ester compound and the agent of acrylic acid series intersection, also can be made up 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, in the case of their total is made as 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 above-mentioned monomer (mm) agent is more than 0.01 quality %, poly-(methyl) acrylate (b1-2) becomes the material with sufficient graft polymerization starting point, if it is below 10 quality %, can maintain the caoutchouc elasticity of poly-(methyl) acrylate (b1-2).
In addition, if the usage quantity of the acrylic acid series linking agent in above-mentioned monomer (mm) is below 10 quality %, can maintain the caoutchouc elasticity of poly-(methyl) acrylate (b1-2).
In the situation that above-mentioned organopolysiloxane (b1-1) is made as to 100 mass parts, usage quantity for the monomer (mm) of polymerization under the existence of above-mentioned organopolysiloxane (b1-1) is preferably 400～9,900 mass parts, more preferably 900～1,900 mass parts.The usage quantity of above-mentioned monomer (mm), in the time of above-mentioned scope, can obtain the compounded rubber (b1) of the products formed that gives shock resistance and bright property excellence efficiently.
Stating in the use organopolysiloxane (b1-1) and monomer (mm) manufactures in the situation of compounded rubber (b1), can enumerate and for example in the latex that contains organopolysiloxane (b1-1), add as required after water, polymerization starter, emulsifying agent, chain-transfer agent (molecular weight regulator) etc., supply with monomer (mm) while the method for carrying out polymerization.Now, the supply of monomer (mm) can once or separately be carried out, and can carry out continuously.
Now, the monomer (mm) of supplying with can directly use, the emulsification that maybe can adopt use contains monomer (mm), emulsifying agent and water in advance mixture to prepare.In the latter's situation, can use the emulsification that monomer (mm) is carried out to 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 to 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, in the time of above-mentioned scope, can be manufactured compounded rubber (b1) efficiently, in addition, the products formed obtaining can be made to 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 can stably keep letex polymerization time, improves polymerisation conversion.In addition, as mentioned emulsifier, can use the emulsifying agent identical with the emulsifying agent of the manufacture for above-mentioned organopolysiloxane (b1-1).
Polymerization temperature when above-mentioned monomer (mm) is carried out to polymerization is generally 65 DEG C～98 DEG C, is preferably 70 DEG C～95 DEG C.In addition, polymerization time is generally 0.5～6 hour.
The volume average particle size of the compounded rubber (b1) obtaining 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 more than gel content is preferably 70 quality %, more preferably more than 90 quality %, more than being particularly preferably 95 quality %, toluene swell degree is preferably 2～30 times, more preferably 6～25 times.
The compounded rubber (b1) obtaining as described above becomes in organopolysiloxane (b1-1), to contain from form or the organopolysiloxane (b1-1) of the grafting compound of poly-(methyl) acrylate (b1-2) grafting of the structural unit of above-mentioned monomer (mm) and contain from poly-(methyl) acrylate (b1-2) of the structural unit of above-mentioned monomer (mm) and forms the cross-linked network that is mutually wound around, 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, for hypertrophy processing.
The second-order transition temperature that contains homopolymer for the ethene base system monomer (b2) of the formation of mentioned component [B] exceedes (methyl) acrylic acid alkyl ester compound, aromatic ethenyl compound and the vinyl cyanide based compound of 0 DEG C.
Exceed (methyl) acrylic acid alkyl ester compound of 0 DEG C as the second-order transition temperature 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 in above-mentioned ethene base system monomer (a2), can use.
In above-mentioned ethene base system monomer (b2), second-order transition temperature contained, homopolymer exceedes the ratio of (methyl) acrylic acid alkyl ester compound of 0 DEG C, from the viewpoint of the shock resistance of products formed and the balance of bright property, in the case of the total of (methyl) acrylic acid alkyl ester compound, aromatic ethenyl compound and vinyl cyanide based compound is made as 100 quality %, be preferably 40～60 quality %.
In addition, the ratio of the usage quantity of contained aromatic ethenyl compound and vinyl cyanide based compound in above-mentioned ethene base system monomer (b2), in the case of both totals are made as 100 quality %, be preferably respectively 10～90 quality % and 10～90 quality %.
With respect to the total amount of above-mentioned ethene base system monomer (b2), the ratio that in above-mentioned ethene base system monomer (b2), second-order transition temperature contained, homopolymer exceedes the total amount of (methyl) acrylic acid alkyl ester compound, aromatic ethenyl compound and the vinyl cyanide based compound of 0 DEG C is preferably 70～100 quality %, more preferably 85～100 quality %.
Above-mentioned ethene base system monomer (b2) can be exceeded by the second-order transition temperature of homopolymer (methyl) acrylic acid alkyl ester compound of 0 DEG C, aromatic ethenyl compound and vinyl cyanide based compound form, also (second-order transition temperature of homopolymer is 0 DEG C of following (methyl) acrylic compound can also to contain other monomers, maleimide amine compound, unsaturated acid anhydride, containing carboxyl unsaturated compound, hydroxyl unsaturated compound, containing amino unsaturated compound, containing amido unsaturated compound, containing epoxy group(ing) unsaturated compound, contain azoles quinoline base unsaturated compound etc.).And, as other monomers, in the situation that containing maleimide amine compound, with use acrylic rubber matter polymkeric substance (a1) manufacture composition [A] situation similarly, sometimes contain from the multipolymer of the structural unit of maleimide amine compound and form as graftomer not, therefore, contain in situation about generating from the multipolymer of the structural unit of maleimide amine compound, this multipolymer is included in composition [C].
For the compounded rubber (b1) of manufacture of mentioned component [B] and the ratio of the usage quantity of ethene base system monomer (b2), from the viewpoint of the shock resistance of products formed and the balance of bright property, in the case of both totals being made as 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: under the existence of compounded rubber (b1), supply with a part for ethene base system monomer (b2) and carry out polymerization, the method for supplying with thereafter remainder and carrying out polymerization; Under the existence of compounded rubber (b1), supply with the total amount of ethene base system monomer (b2) and carry out method of polymerization etc.In the present invention, preferably the former method, particularly, (methyl) acrylic acid alkyl ester compound that can the second-order transition temperature of homopolymer be exceeded to 0 DEG C under the existence of compounded rubber (b1) is carried out graft polymerization, adds thereafter not containing maleimide amine compound, the ethene base system monomer that contains aromatic ethenyl compound and vinyl cyanide based compound and carries out polymerization.Use when carrying out like this composition [B] that the using method of ethene base system monomer (b2) obtains, can obtain the excellent especially products formed of shock resistance and bright property.
Graft polymerization can be 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].
From the viewpoint of forming process, shock resistance, bright property etc., percentage of grafting in mentioned component [B], be preferably 5～200 quality % in containing from the ratio of the multipolymer of the structural unit of ethene base system monomer (b2) of the upper grafting of compounded rubber (b1), more preferably 10～150 quality %, more preferably 20～120 quality %.When percentage of grafting is too low, the shock resistance of products formed is insufficient sometimes.On the other hand, when percentage of grafting is too high, forming process is insufficient sometimes.
Mentioned component [C] is for containing structural unit from maleimide amine compound (hereinafter referred to as " structural unit (c1) " with respect to entire infrastructure unit.) 10～70 quality %, preferably 20～70 quality %, the further preferred maleimide based copolymer of 25～65 quality %.The content of said structure unit (c1), in the time of above-mentioned scope, can obtain the products formed of thermotolerance and shock resistance excellence.
In addition, in the case of mentioned component [A] for by acrylic rubber matter polymkeric substance portion and the situation that contains the graft resin forming from the multipolymer portion of the structural unit (c1) of maleimide amine compound and mentioned component [B] for by compounded rubber portion with contain the graft resin forming from the multipolymer portion of the structural unit (c1) of maleimide amine compound, these graft resins are not included in composition [C]., this composition [C] for structurally with mentioned component [A] and [B] independently composition.
In addition, mentioned component [C] can be for to contain the only multipolymer of a kind of structural unit (c1), also can be for containing multipolymer of more than two kinds.
The multipolymer of mentioned component [C] for containing structural unit (c1), further contains other structural units (hereinafter referred to as " structural unit (c2) ".)。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, containing carboxyl unsaturated compound, hydroxyl unsaturated compound, containing amino unsaturated compound, containing amido unsaturated compound, containing epoxy group(ing) unsaturated compound, contain azoles quinoline base unsaturated compound etc.These compounds are suitable for as the illustrative compound of ethene base system monomer (a2) of formation that can be used in mentioned component [A].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 maleimide amine compound, preferably N-phenylmaleimide, as aromatic ethenyl compound, optimization styrene, as vinyl cyanide based compound, preferably vinyl cyanide, as unsaturated acid anhydride, preferably 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 DEG C～250 DEG C, more preferably 120 DEG C～230 DEG C.When this second-order transition temperature is too high, forming process, shock resistance become insufficient sometimes, in the time that it is too low, 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 methyl ethyl ketone, 30 DEG C) is preferably 0.1～1.5dl/g, more preferably 0.15～1.0dl/g.
Above-mentioned limiting viscosity, by making mentioned component [C] be dissolved in methyl ethyl ketone, is adjusted 5 solution that concentration is different, measures the reduced viscosity of each concentration obtain with Ubbelohde viscosity tube at 30 DEG C.
The kind of polymerization starter that above-mentioned limiting viscosity can be used when being adjusted at manufacture 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 forming when mentioned component [C] can come comfortable manufacture mentioned component [A] or composition [B], the multipolymer that also can be combined with other preparation forms.In the latter's situation, can be use 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.
As other manufacture method of mentioned component [C], can enumerate and make not containing maleimide amine compound, the ethene base system monomer copolymerization that 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 ".), the method for the multipolymer that manufacture contains structural unit (c1).
As the primary amine 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-bis- 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 DEG C～350 DEG C, more preferably 100 DEG C～300 DEG C.
Above-mentioned imidization reaction may not need the existence of catalyzer.Use in the situation of catalyzer preferably 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 containing the structural unit being selected from from aromatic ethenyl compound (below also referred to as " structural unit (d1) " as any composition.), from the structural unit of vinyl cyanide based compound (below also referred to as " structural unit (d2) ".) and from the structural unit of (methyl) acrylic acid alkyl ester compound (below also referred to as " structural unit (d3) ".) at least a kind of structural unit and do not describe containing the composition [D] of the polymkeric substance of the structural unit from maleimide amine compound.
In addition, this composition [D] can contain from unsaturated acid anhydride, containing carboxyl unsaturated compound, hydroxyl unsaturated compound, contains amino unsaturated compound, contains amido unsaturated compound, contains 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, containing carboxyl unsaturated compound, hydroxyl unsaturated compound, containing amino unsaturated compound, containing amido unsaturated compound, containing epoxy group(ing) unsaturated compound and contain azoles quinoline base unsaturated compound is suitable for as the illustrative compound of ethene base system monomer (a2) of formation that can be used in mentioned component [A].And these compounds may be used singly or in combination of two or more.
Be by acrylic rubber matter polymkeric substance portion with not containing the structural unit (c1) from maleimide amine compound at mentioned component [A], contain said structure unit (d1), (d2), etc. (d3) situation of the graft resin that (being total to) polymkeric substance portion forms and mentioned component [B] be by compounded rubber portion and do not contain the structural unit (c1) from maleimide amine compound, contain said structure unit (d1), (d2), etc. (d3) in the situation of the graft resin that (being total to) polymkeric substance portion forms, these graft resins are not included in composition [D]., this composition [D] for structurally with mentioned component [A] and [B] independently composition.
In the situation that composition of the present invention contains composition [D], the products formed of the appearance of the products formed that can make forming process excellence, obtains and shock resistance excellence.
As mentioned component [D], below illustrate.
(D1) by structural unit (d1) and (d2) form multipolymer (multipolymer of aromatic ethenyl compound and vinyl cyanide based compound).
(D2) multipolymer multipolymer of (aromatic ethenyl compound and (methyl) acrylic compound) by structural unit (d1) and (d3) forming.
(D3) multipolymer (multipolymer of aromatic ethenyl compound, vinyl cyanide based compound and (methyl) acrylic compound) by structural unit (d1), (d2) and (d3) forming.
(D4) (being total to) polymkeric substance ((being total to) polymkeric substance of (methyl) acrylic compound) being formed by structural unit (d3).
Wherein, from the viewpoint of forming process, appearance and shock resistance, particularly preferably form (D1) and multipolymer (D3).
In addition, mentioned component [D] is in the situation of multipolymer of above-mentioned form (D1), structural unit (d1) and (d2) containing proportional, in the case of both totals being made as 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 (d3) containing proportional, in the case of their total being made as 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 forming process, the thermotolerance of products formed obtaining and the viewpoint of appearance, the limiting viscosity of mentioned component [D] (in methyl ethyl ketone, 30 DEG C) 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 polymerization starter that above-mentioned limiting viscosity can be used when being adjusted at manufacture 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 forming when mentioned component [D] can come comfortable manufacture mentioned component [A] or composition [B], also can coordinate the multipolymer of other preparation.In the latter's situation, can use and contain the ethene base system monomer of at least a kind being 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 not composition containing composition [D], therefore, and the composition of preferred composition for containing 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.
In the situation that composition of the present invention contains other thermoplastic resins, the upper limit of its content, in the case of the total amount of mentioned component [A], [B], [C] and [D] is made as 100 mass parts, 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 rubber polymer (a1) and the content of above-mentioned compounded rubber (b1), in the case of the total of mentioned component [A], [B], [C] and [D] is made as 100 quality %, be 8～35 quality %, be preferably 12～32 quality %, more preferably 15～28 quality %.The ratio of above-mentioned total amount, in the time of above-mentioned scope, can obtain the products formed that thermotolerance, shock resistance, molded appearance etc. are excellent.
In addition, in composition of the present invention, from the content of the structural unit of maleimide amine compound, in the case of the total that forms the structural unit of mentioned component [A], the structural unit that forms mentioned component [B], the structural unit of formation mentioned component [C] and the structural unit of formation mentioned component [D] is made as 100 quality %, 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, in the time of above-mentioned scope, can obtain the excellent products formed such as thermotolerance, molded appearance, bright property.
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].As the latter's example, for following situation: composition [A] is for carrying out by the ethene base system monomer (a2) that contains aromatic ethenyl compound and vinyl cyanide based compound and maleimide amine compound the graft resin that polymerization obtains under the existence at acrylic rubber matter polymkeric substance (a1), and the situation from the structural unit of maleimide amine compound is contained in the multipolymer portion in this graft resin; And composition [B] is for carrying out by the ethene base system monomer (b2) that contains aromatic ethenyl compound and vinyl cyanide based compound and maleimide amine compound the graft resin that polymerization obtains under the existence at compounded rubber (b1), the situation from the structural unit of maleimide amine compound is contained in the multipolymer portion 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, in the case of both totals being made as 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 excellence, the generation of wire drawing when 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], from the viewpoint of the forming process of composition and the shock resistance of products formed, thermotolerance, molded appearance and bright property, in the case of the total of mentioned component [A], [B], [C] and [D] is made as 100 quality %, 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], from the viewpoint of shock resistance, thermotolerance, molded appearance and the bright property of products formed, in the case of the total of mentioned component [A], [B], [C] and [D] is made as 100 quality %, be preferably 10～90 quality %, more preferably 15～70 quality %, are particularly preferably 15～60 quality %.
In the situation that lampshade of the present invention contains mentioned component [D] with thermoplastic resin composition, the ratio of the content of this composition [D], in the case of the total of mentioned component [A], [B], [C] and [D] is made as 100 quality %, be preferably below 80 quality %, more preferably 15～70 quality %, are particularly preferably 20～65 quality %.When the content of mentioned component [D] exceedes 80 quality %, thermotolerance and shock resistance become insufficient sometimes.
In the situation that composition of the present invention contains mentioned component [D], from the viewpoint of the forming process of composition and the thermotolerance of products formed, shock resistance and aesthetic appearance, the limiting viscosity of the mixture of mentioned component [C] and [D] (in methyl ethyl ketone, 30 DEG C) 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 in composition of the present invention, to be equivalent to the not composition of graftomer.In the situation that reclaiming these compositions, be suitable for composition of the present invention is dropped in acetone, use after bobbing machine vibration (23 DEG C, 2 hours), use separating centrifuge to carry out centrifugation (0 DEG C of temperature, revolution 28,000rpm, 1 hour), the method etc. of removing thereafter acetone from the solvable composition of acetone reclaiming.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 is (below also referred to as " raw material [R] " by the raw material that contains following component.) composition that is obtained by mixing is (hereinafter referred to as " composition [X] ".), described component is: [S] contains in aforesaid propylene acid is under the existence of rubber polymer (a1), by the rubber reinforced resin of the acrylic rubber matter enhancing by polymer graft resin not obtaining containing maleimide amine compound, the ethene base system monomer that comprises aromatic ethenyl compound and vinyl cyanide based compound carry out polymerization (below also referred to as " raw material [S] ".), [T] contains under the existence of above-mentioned compounded rubber (b1), (methyl) acrylic acid alkyl ester compound that the second-order transition temperature of homopolymer is exceeded to 0 DEG C is carried out polymerization, follows the rubber reinforced resin of the compounded rubber enhancing graft resin that the ethene base system monomer that does not contain maleimide amine compound, comprises aromatic ethenyl compound and vinyl cyanide based compound is carried out to polymerization and obtain (below also referred to as " raw material [T] ".), and [U] with respect to entire infrastructure unit contain 10～70 quality % from the maleimide based copolymer of the structural unit of maleimide amine compound (below 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], for to contain under the existence of acrylic rubber matter polymkeric substance (a1), (can contain (methyl) acrylic acid alkyl ester compound by the ethene base system monomer that does not contain maleimide amine compound, comprises aromatic ethenyl compound and vinyl cyanide based compound.) carry out polymerization and the acrylic rubber matter enhancing by polymer graft resin that obtains (below 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 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] exceedes the second-order transition temperature of homopolymer (methyl) acrylic acid alkyl ester compound of 0 DEG C and carries out polymerization for containing under the existence of compounded rubber (b1), then will not contain 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, conventionally, the multipolymer of above-mentioned each monomer contains the compounded rubber forming in the upper grafting of above-mentioned compounded rubber (b1) and strengthens graft resin (below 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 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 mentioned component [C], can directly use pre-prepd maleimide based copolymer.
Above-mentioned composition [X], as polymkeric substance or resin contained in above-mentioned raw materials [R], for using in the situation of the composition that above-mentioned raw materials [S], [T] and [U] obtain, the ratio of the content of these in above-mentioned raw materials [R], in the case of 3 total being made as 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 use each composition in above-mentioned scope, can obtain thermotolerance, shock resistance, molded appearance, vibrate the products formed of deposited property and bright property excellence.
In addition, above-mentioned raw materials [R] also can be combined with (being total to) polymkeric substance that is equivalent to mentioned component [D] in addition (hereinafter referred to as " (being total to) polymkeric substance [V] ".)。As this (being total to) polymkeric substance [V], can be used 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 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, in the case of 4 total being made as 100 quality %, be preferably respectively 1～88 quality %, 1～88 quality %, 10～89 quality % and 1～80 quality %, more preferably 8～50 quality %, 2～40 quality %, 10～40 quality % and 5～60 quality %, be particularly preferably 8～42 quality %, 2～30 quality %, 10～40 quality and 20～50 quality %.By use each composition in above-mentioned scope, can obtain thermotolerance, shock resistance, molded appearance, vibrate the products formed of deposited property and bright property excellence.
Above-mentioned composition [X] is obtained by mixing raw material [R], in the case of utilizing identical polymerization process to obtain raw material [S], [T] and [U] (and (being total to) polymkeric substance [V]), can be formed in latex or resin solution by graft resin (Ar), graft resin (Br), raw material [U], multipolymer (Dr1) and resin compound that (Dr2) (and (being total to) polymkeric substance [V]) forms, can make the composition that its recovery is obtained.
The form of composition of the present invention is not particularly limited, and is preferably melting mixing thing.Therefore,, in the situation that above-mentioned composition [X] is made to melting mixing thing, be suitable for the method etc. that above-mentioned raw materials [R] is used to mixing rolls such as single screw extrusion machine, twin screw extruder, Banbury mixer, pressurization kneader and (two) roller etc.When mixing, can by form above-mentioned raw materials [R] each composition once mixing, also can separate cooperation while mixing.In addition, after using Banbury mixer, kneader etc. mixing, also can utilize forcing machine granulation.Melting temperature is preferably 200 DEG C～300 DEG C, more preferably 220 DEG C～280 DEG C.
In composition of the present invention, as other thermoplastic resins that can coordinate, can enumerate: under the existence of other rubber polymers except acrylic rubber matter polymkeric substance (a1) and compounded rubber (b1), ethene base system monomer is carried out to polymerization and rubber reinforced resin such as ABS resin, AES resin of obtaining, polyamide resin, polycarbonate resin, vibrin, polyphenylene oxide resin etc.These can contain separately, also can contain two or more.
In composition of the present invention, as the additive that can coordinate, 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 thermoplastic resin composition.Directly evaporation is for undercoat is not set, the direct method of the evaporation layer by 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 of Pa left and right, products formed is set, makes the deposition material that gasifies in this container or distil be attached to the surface of products formed, form evaporation layer.In the situation that making 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, the processing that also can by RF plasma body, ion gun irradiation etc., adaptation be improved in advance to the products formed before evaporation, according to composition of the present invention, can omit this processing to the products formed obtaining.
In addition, lampshade of the present invention is preferably the molding material of the products formed that is suitable for the deposited method of vibration with thermoplastic resin composition.
Vibrating deposited method is following method: use composition of the present invention to form a resin component, use composition of the present invention or other compositions to form after another resin components 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, by the bonding resinous principle melting with 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, making to vibrate between products formed deposited in the situation that, suppress the generation of wire drawing, therefore do not damage the aesthetic appearance of joint product.
Products formed of the present invention is the products formed (lampshade etc.) that uses the composition of the invention described above to obtain.The composition that, products formed of the present invention contains the invention described above.
Due to the forming process excellence of composition, be therefore 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 in the situation of formation etc. of undercoat, can implement utilize the directly metalized of vapour deposition method such as vacuum vapour deposition, sputtering method to its surface.
Carry out the products formed of metalized, its bright property excellence.And this surface can be former state, but in order to protect its generation, oxidative degradation etc. of avoiding the scar that such as dust etc. causes, can be by the forming surface such as application, plasma polymerization coating.
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 evaluate 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 latex and number average bead diameter (Mn) use HONEYWELL society system " マ イ Network ロ ト ラ ッ Network UPA150 ", at 25 DEG C, 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
Toluene swell degree and the method below gel content utilization are obtained.
Approximately 0.2 gram that weighs acrylic rubber matter polymkeric substance (is designated as Wr by quality.), drop in toluene 25ml, stir lightly., 25 DEG C at place 48 hour, use the 200 object wire nettings that weigh in advance (quality to be designated as to Wm gram thereafter.) filter, be separated into insoluble point and solvable point.After separation, weigh (quality is designated as to W1 gram) by insoluble point with together with the wire netting of filtering separation rapidly, deducted the weighing value (Wm) of wire netting by this weighing value (W1), obtain (quality being designated as to Ws gram by the weighing value of insoluble point of toluene swell.)。Then, owing to containing toluene with in insoluble point of toluene swell, therefore by its at 25 DEG C air-dry 12 hours, continue to use Vacuumdrier at 60 DEG C dry 12 hours, remove dry toluene contained in insoluble point thus.Dried insoluble point is weighed and (quality be designated as to W2 gram together with wire netting.), being deducted the weighing value (Wm) of wire netting by this weighing value (W2), the dry weight that obtains insoluble point (is designated as Wd gram by 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, be to stir 15% calcium chloride water while drip the latex that contains above-mentioned polymkeric substance for the acrylic rubber matter polymkeric substance of measuring, polymkeric substance is solidified and wash, the dry and solid rubber that obtains.
(3) percentage of grafting
A certain amount of (x gram) of the rubber reinforced resin (S) that uses acrylic rubber matter polymkeric substance to obtain dropped in acetone, use bobbing machine vibration 2 hours, (being total to) polymkeric substance (not graftomer=acetone soluble polymer) dissociating is dissolved.,, this liquid is used to centrifuge separator thereafter, with 28,000rpm centrifugation 1 hour.The insoluble throw out obtaining is used to Vacuumdrier, at 120 DEG C, is dried 2 hours, weigh insoluble point of (graft resin) (y gram).When the amount of acrylic rubber matter polymkeric substance contained in x gram of above-mentioned rubber reinforced resin (S) is designated as to xr gram, utilize following formula to calculate percentage of grafting.Replace acrylic rubber matter polymkeric substance, the situation of the rubber reinforced resin (T) that use compounded rubber obtains is calculated similarly.
Percentage of grafting (%)=[(y-xr) ÷ xr] × 100
(4) limiting viscosity
To the rubber reinforced resin (T) obtaining in the rubber reinforced resin obtaining in synthesis example 2-1～2-11 (S) and synthesis example 2-12, measure the not limiting viscosity of graftomer (acetone soluble polymer).In addition, also measure the limiting viscosity of the acetone soluble polymer being obtained by composition material composition is mixing and that obtain.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 DEG C.
(7) appearance (current mark, color spot, gloss)
In the time evaluating surperficial aesthetic appearance, as tinting material, use with respect to the composition of recording in table and further coordinate 0.2 part of Sakai chemistry society's calcium stearate processed " SC-100 " (trade(brand)name) and 0.5 part of society of Mitsubishi Chemical charcoal processing black " RCF-#45 " (trade(brand)name) and the composition that obtains.
Said composition is supplied to Jing Resin Industry society electric injection moulding machine processed " エ Le ジ ェ Network ト NEX30 " (trade(brand)name), carry out injection molding (220 DEG C～260 DEG C of resin temperatures, 50 DEG C of die temperatures), obtain the flat black products formed (thering is the side gate of 4mm × 1mm in the central authorities on a limit of 55mm) of 80mm × 55mm × 2.4mm.
The surface of this products formed of visual observation, judges aesthetic appearance with following benchmark.
◎: gloss excellence, do not see current mark and color spot.
Zero: gloss is good, almost do not 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 that will be used for the appearance of evaluating above-mentioned (7) is supplied with toshiba machine society injection moulding machine processed " IS-170FA " (model name), carry out injection molding (220 DEG C～260 DEG C of resin temperatures), the lampshade 12 on curved surface with peristome is carried out to moulding (with reference to Fig. 2).The unit of the size in accompanying drawing is " mm ".
On the other hand, as by adhesion material, metha crylic resin processed mitsubishi rayon society " ア Network リ ペ ッ ト VH-4 " (trade(brand)name) is supplied with to injection moulding machine, carry out injection molding (220 DEG C～270 DEG C of resin temperatures), obtain the lamp lens 11 (with reference to Fig. 1) of regulation shape.
,, lamp lens 11 and lampshade 12 are utilized to the moving cladding machine " BURANSON2407 " (model name) of Japanese エ マ ソ Application society's damping thereafter, vibrate according to Fig. 3 deposited.Fig. 3 is the accompanying drawing that represents the deposited position of 2 parts, under the following conditions, the circumference of the peristome of the lampshade 12a of B-B ' the line section in downward jut and the presentation graphs 2 of the lamp lens 11a of A-A ' the line section in presentation graphs 1 is carried out deposited.In the time that this vibration is deposited, the radical (radical of thread the wire drawing more than 2mm producing in lampshade) of the number of counting tree cosmetics body (produce in lampshade and can by the number of the resin powder about the tens of micron～2mm of Visual Confirmation) and wire drawing.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.Wire drawing number is below 5.
△: the number of resin powder is 6～10.Wire drawing number is 6～10.
×: the number of resin powder is more than 11.Wire drawing number is more than 11.
< vibrates deposited condition >
(i) the deposited condition of powder amount evaluation use
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 use
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
To be used for evaluating above-mentioned (7) appearance black combination supply with toshiba machine society injection moulding machine processed " IS-170FA " (model name), carry out injection molding (220 DEG C～260 DEG C 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 when film forming
< plasma polymerization condition >
Import gas HMDS 30sccm
Vacuum tightness 1.5Pa when polymerization
To the bright property evaluation formed body obtaining, use Tokyo electricity Se society system numeral albedometer " TR-1100AD " (model name) to measure diffuse reflectance.Unit is %.
2. manufacture raw material
Synthesizing of 2-1. acrylic rubber matter polymkeric substance
First, the synthetic method for the manufacture of the acrylic rubber matter polymkeric substance 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 to " BA ".) 91.3 parts and allyl methacrylate(AMA) (be designated hereinafter simply as " AMA ".) 0.7 part mix, prepare monomer mixture (I).
In addition, in 99 parts, water, dissolve Potassium Persulphate and (be designated hereinafter simply as " KPS ".) 1 part, prepare the polymerization starter aqueous solution and (be abbreviated as below " 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 150 parts, water into, (be abbreviated as below " SDBS " as the Sodium dodecylbenzene sulfonate of emulsifying agent.) 0.5 part and BA8 part.On one side stirring system in, on one side under nitrogen gas stream reaction system heated, thereafter.In the time that internal temperature reaches 65 DEG C, to adding and (be abbreviated as below " PHS " as electrolytical V-Brite B in reactor.) 0.03 part, thereafter, reaction system is heated.
In the time that internal temperature reaches 75 DEG C, pack 7 parts of the OXI aqueous solution (I) into, in synthermal lower beginning polymerization.In the moment starting from polymerization through 1 hour, finish the reaction of the 1st polymerization process.In addition, the polymerisation conversion 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 obtaining is 61nm.
(3) the 2nd polymerization process
7 parts of 1/3rd and the OXI aqueous solution (I) in the reactor that contains above-mentioned latex, adding monomer mixture (I) start polymerization at 75 DEG C.Start 1 hour from polymerization, in the time that the internal temperature of reactor reaches 75 DEG C, 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 in the time that the internal temperature of reactor reaches 75 DEG C, 7 parts of the monomer mixture (I) of supply residue 1/3rd and the OXI aqueous solution (I), proceed polymerization.It finished polyreaction after 1 hour, obtained the latex that contains acrylic rubber matter polymkeric substance (a1-1).
The polymerisation conversion when 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 obtaining is 133nm, and size distribution Mv/Mn is 1.03.In addition, toluene swell degree is 15, and gel content is 90.0%.Result more than shown in table 1.
Synthesis example 1-2
In the 1st polymerization process, except 0.5 part of interpolation sodium bicarbonate, similarly obtain with synthesis example 1-1 the latex that contains acrylic rubber matter polymkeric substance (a1-2).
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 obtaining 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, toluene swell degree is 21, and gel content is 82.0%.Result more than shown in table 1.
Synthesis example 1-3
(1) preparation of liquid
BA79 part and AMA1 part are mixed, prepare monomer mixture (II).
In addition, in 10 parts, water, dissolve Calcium Disodium Versenate and (be abbreviated as below " EDTA ".) 0.01 part, ferrous sulfate (be abbreviated as " FES " below.) 0.002 part and rongalite (write a Chinese character in simplified form hydrogen below for " NFS ".) 0.3 part, preparing sulfoxylic acid hydrogen salt is that the reductive agent aqueous solution (is abbreviated as " the SFS aqueous solution (I) " below.)。
And dissolved hydrogen dicumyl peroxide (is abbreviated as " CHP " below in 30 parts, water.) 0.025 part, prepare the polymerization starter aqueous solution and (be abbreviated as below " 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, water, SDBS2.0 part and BA20 part.On one side stirring system on one side under nitrogen gas stream reaction system heated, thereafter.In the time that internal temperature reaches 60 DEG C, in reactor, add 85% point and 30% point of the CAT aqueous solution (I) of the SFS aqueous solution (I), in synthermal lower beginning polymerization.In the moment starting from polymerization through 1 hour, finish the reaction of the 1st polymerization process.In addition, the polymerisation conversion 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 obtaining is 51nm.
(3) the 2nd polymerization process
In the reactor that contains above-mentioned latex, add 15% point of the residue of the SFS aqueous solution (I), thereafter at once, all, through 40% point of 1 hour 30 minutes continuous adding monomer mixtures (II) 70% point and the CAT aqueous solution (I), start polymerization.During this time, the internal temperature of reactor remains on 60 DEG C.After interpolation finishes, synthermal lower slaking 30 minutes.(start 2 hours from polymerization) thereafter, all through 1 hour continuous adding monomer mixture (II) 30% point of residue and 30% point of the residue of the CAT aqueous solution (I), proceed polymerization.Add and finish rear (starting 3 hours from polymerization), after 1 hour, finish polyreaction in synthermal lower slaking, obtain the latex that contains acrylic rubber matter polymkeric substance (a1-3).
The polymerisation conversion when 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 obtaining is 93nm, and size distribution Mv/Mn is 1.06.In addition, toluene swell degree is 7, and gel content is 98.5%.Result more than shown in table 1.
Synthesis example 1-4
(1) preparation of liquid
BA99.8 part and AMA0.2 part are mixed, prepare 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, water, dissolve not 1 part of homogenizing potassium rosinate soap and KPS1 part, prepare the polymerization starter aqueous solution and (be abbreviated as below " 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 170 parts, water into, semi-harden tallow fatty acids soda soap (is abbreviated as " SSF " below.) 0.03 part, the sodium salt of beta-naphthalenesulfonic-acid formalin polycondensate (be abbreviated as " PNF salt " below.) 1.0 parts, as 1.0 parts of electrolytical sodium bicarbonates and monomer mixture (III) 10% point.,, in the system of stirring on one side, under nitrogen gas stream, internal temperature is warming up to 65 DEG C on one side thereafter.In the time reaching 65 DEG C, add PHS0.005 part, thereafter, reaction system is heated.
In the time that internal temperature reaches 75 DEG C, add 7 parts of the OXI aqueous solution (I), in synthermal lower beginning polymerization.In the moment starting from polymerization through 1 hour, finish the reaction of the 1st polymerization process.In addition, the polymerisation conversion 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 obtaining is 112nm.
(3) the 2nd polymerization process
In the reactor that contains above-mentioned latex, all through 4 hours continuous adding monomer mixture (III) 90% point of residue and 10 parts of the OXI aqueous solution (II), start polymerization.During this time, the temperature of reaction system remains on 75 DEG C.After interpolation finishes, the temperature of reaction system was warming up to 80 DEG C with 30 minutes.Then, slaking 1 hour at this temperature, finishes polyreaction, obtains the latex that contains acrylic rubber matter polymkeric substance (a1-4).
The polymerisation conversion when 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 obtaining is 192nm, and size distribution Mv/Mn is 1.09.In addition, toluene swell degree is 32, and gel content is 41%.Result more than shown in table 1.
Synthesis example 1-5
In the 1st polymerization process, the usage quantity that makes to add the SDBS in reactor is 0.1 part, in addition, and is used as 1.5 parts, electrolytical PHS0.03 part and sodium carbonate, in addition, similarly obtain with synthesis example 1-1 the latex that contains acrylic rubber matter polymkeric substance (a1-5).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 obtaining 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, toluene swell degree is 18, and gel content is 89.6%.Result more than shown in table 1.
Synthesis example 1-6
(1) preparation of liquid
By BA100 part and 0.3 part of mixing of triallyl cyanurate, prepare monomer mixture (IV).
In addition, as the polymerization starter aqueous solution, use the OXI aqueous solution (I) of preparing in synthesis example 1-1.
(2) manufacture 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 200 parts, water, SSF1.5 part and trisodium phosphate into and (be abbreviated as below " SPP ".) 0.3 part.On one side stirring system on one side under nitrogen gas stream reaction system heated, thereafter.In the time that internal temperature reaches 80 DEG C, 30 parts of 100.3 parts of monomer mixtures (IV) and the OXI aqueous solution (I) were all supplied to reactor continuously through 4 hours, carry out polymerization.During this time, the internal temperature of reactor remains on 80 DEG C.After the interpolation of whole liquids finishes, further at 80 DEG C, keep making for 1 hour its slaking, thereafter, finish polyreaction.Polymerisation conversion is now 97.8%, and in the latex obtaining, the volume average particle size (Mv) of contained acrylic rubber matter polymkeric substance is 87nm.In addition, toluene swell degree is 8, and gel content is 89%.
Then, utilize the method for recording in TOHKEMY 2003-138089 communique to carry out the particle diameter hypertrophyization processing that aforesaid propylene acid is rubber polymer.
Add SDSB0.15 part containing in containing the reactor of latex that aforesaid propylene acid is 100 parts of rubber polymers., on one side the internal temperature of reactor remained on to 25 DEG C～30 DEG C, under agitation, through within 30 minutes, adding continuously 60 parts of 5% aqueous acetic acids (particle diameter is loose to be processed) on one side thereafter.Then, after the interpolation of aqueous acetic acid finishes, through within 10 minutes, adding continuously 20 parts of 10% aqueous sodium hydroxide solutions.Thus, obtain the latex of the acrylic rubber matter polymkeric substance (a1-6) that contains particle diameter hypertrophyization.The volume average particle size (Mv) of the acrylic rubber matter polymkeric substance in the latex obtaining is 157nm, and size distribution Mv/Mn is 1.15.Result more than shown in table 1.
Synthesis example 1-7
In the 1st polymerization process, make to pack into water in reactor and the amount of SDBS and be 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 latex when the 1st polymerization process finishes is 51nm.
The polymerisation conversion when 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 obtaining is 81nm, and size distribution Mv/Mn is 1.04.In addition, toluene swell degree is 15, and gel content is 90.7%.Result more than shown in table 1.
Synthesis example 1-8
In the 1st polymerization process, the amount that makes to pack into the SDBS in reactor is 0.05 part, in the 2nd polymerization process, in the latex that makes to obtain in the 1st operation with monomer mixture (I) 1/3rd together with the amount of the SDBS that packs into be outside 0.45 part, similarly obtain acrylic rubber matter polymkeric substance (a1-8) with synthesis example 1-1.The volume average particle size (Mv) of the rubber polymer particle in latex when the 1st polymerization process finishes is 117nm.
The polymerisation conversion when 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 obtaining is 278nm, and size distribution Mv/Mn is 1.04.In addition, toluene swell degree is 14, and gel content is 91.4%.Result more than shown in table 1.
Synthesis example 1-9
Replace monomer mixture (I) and use outside the monomer mixture being formed by the AMA of the BA of 90 parts and 2 parts, similarly obtaining acrylic rubber matter polymkeric substance (a1-9) with synthesis example 1-1.The volume average particle size (Mv) of the rubber polymer particle in latex when the 1st polymerization process finishes is 54nm.
The polymerisation conversion when 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 obtaining is 116nm, and size distribution Mv/Mn is 1.03.In addition, toluene swell degree is 5, and gel content is 91%.Result more than shown in table 1.
Synthesis example 1-10
Carry out the 1st polymerization process in synthesis example 1-1, in reactor, contain under the state of latex, as the 2nd polymerization process, once add 21 parts of the OXI aqueous solution (I) shown in total amount and the synthesis example 1-1 of the monomer mixture being formed by the AMA of the BA of 91.7 parts and 0.3 part, at 75 DEG C, start polymerization., the internal temperature of reactor remained on to 75 DEG C, carry out the polyreaction of 3 hours, obtain acrylic rubber matter polymkeric substance (a1-10) thereafter.
The polymerisation conversion when 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 obtaining is 121nm, and size distribution Mv/Mn is 1.03.In addition, 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 being formed by the AMA of the BA of 91.95 parts and 0.05 part, similarly obtaining acrylic rubber matter polymkeric substance (a1-11) with synthesis example 1-1.
The volume average particle size (Mv) of the rubber polymer particle in latex when the 1st polymerization process finishes is 72nm, the polymerisation conversion when 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 obtaining is 118nm, and size distribution Mv/Mn is 1.03.In addition, toluene swell degree is 23, and gel content is 64.7%.Table 1 illustrates above result.
[table 1]
Table 1
Synthesizing of 2-2. compounded rubber
Synthesis example 1-12
By 1.96 parts, γ-methacryloxypropyl dimethoxy-methyl silane and 98.04 parts of mixing of organo-siloxane, obtain 100 parts, organo-siloxane mixture.
313 parts of solution that are dissolved with 0.68 part of Sodium dodecylbenzene sulfonate be added on deionized water in 100 parts, this organo-siloxane mixture in, use homogeneous mixer, stir 5 minutes with 10,000rpm.Thereafter, with 300kg/cm 2pressure pass into homogenizer 2 times, by organo-siloxane present latex particulate.
Then, in the removable flask with 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 DEG C, the organo-siloxane latex under agitation, through dropping in 8 hours by corpusculed obtained above., temperature 85 DEG C at maintained 2 hour after, carry out cooling thereafter.
, this reactant with aqueous sodium hydroxide solution neutralized, complete polymerization, obtain the latex that contains organopolysiloxane thereafter.The volume average particle size of organopolysiloxane is 60nm.
The latex obtaining is dried to 30 minutes at 170 DEG C, obtains solids component, 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, the latex that contains organopolysiloxane obtained above (organopolysiloxane is 5.2 parts).Wherein add after 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 forming of t-butyl hydroperoxide, stir 30 minutes, absorbed by organopolysiloxane rubber.
, to removable flask in pass into nitrogen gas stream carry out nitrogen displacement, reaction system is warming up to 55 DEG C thereafter.In the time that fluid temperature reaches 55 DEG C, add and make 0.0001 part, 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 form of rongalite, start radical polymerization.By the polymerization of above-mentioned monomer mixed solution, fluid temperature rises to 92 DEG C.This state is maintained to 1 hour, complete the polymerization of monomer, obtain the latex that contains compounded rubber (b1-1).The volume average particle size of the compounded rubber (b1-1) obtaining is 84nm.
Synthesizing of the rubber reinforced resin that 2-3. contains 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 obtaining in above-mentioned synthesis example 1-1～1-11 is shown.
Synthesis example 2-1
(1) preparation of liquid
Vinylbenzene (is abbreviated as to " ST " below.) 73 parts, vinyl cyanide (are abbreviated as " AN " below.) 27 parts and (be abbreviated as below " TDM " as the tertiary lauryl mercaptan of chain-transfer agent.) 0.3 part of mixing, prepare monomer mixture (V).
In addition, in 100 parts, water, dissolve EDTA0.05 part, FES0.005 part and NFS0.25 part, preparing sulfoxylic acid hydrogen salt is that the reductive agent aqueous solution (is abbreviated as " the SFS aqueous solution (II) " below.)。
And dissolved hydrogen tert-butyl peroxide (is abbreviated as " BHP " below in 50 parts, water.) 0.25 part, prepare the polymerization starter aqueous solution and (be abbreviated as below " 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 100 parts, water, 100 parts, acrylic rubber matter polymkeric substance (a1-1), potassium hydroxide into and (be abbreviated as below " KOH ".) 0.4 part, SDBS3 part and monomer mixture (V) 25% point.On one side stirring system in, on one side under nitrogen gas stream reaction system heated, thereafter.In the time that internal temperature reaches 65 DEG C, by 50% point of the SFS aqueous solution (II) 30% point of supplied reactor with the CAT aqueous solution (II), start polymerization.Start to be warming up to 75 DEG C with 1 hour from polymerization on one side, carry out polyreaction on one side.
Start 1 hour from polymerization, in the time that internal temperature reaches 75 DEG C, all, through within 4 hours, supplying with continuously 70% point of 50% point of the residue of 75% point of residue, the SFS aqueous solution (II) of monomer mixture (V) and the residue of the CAT aqueous solution (II), proceed polymerization.During this time, the temperature of reaction system remains on 75 DEG C.After the interpolation of whole liquids finishes, further at 75 DEG C, keep within 1 hour, making after its slaking, finish polyreaction.Thus, obtain containing the latex by acrylic rubber matter enhancing by polymer graft resin and the rubber reinforced resin (S-1) that graftomer does not form.
Then, in this latex, add magnesium sulfate (peptizer), rubber reinforced resin (S-1) is solidified., wash and be dried, reclaim rubber reinforced resin (S-1) thereafter.The limiting viscosity of percentage of grafting shown in table 2 and not graftomer.
Synthesis example 2-2～2-5
The kind of the matter of acrylic rubber shown in table 2 polymkeric substance and the composition of usage quantity and monomer mixture thereof, in addition, similarly obtain rubber reinforced resin (S-2)～(S-5) with synthesis example 2-1.By percentage of grafting and not the limiting viscosity of graftomer be recorded in table 2 simultaneously.
Synthesis example 2-6
(1) preparation of liquid
ST28 part and AN12 part are mixed, prepare monomer mixture (VI).
In addition, in 10 parts, water, dissolve SPP0.02 part, FES0.004 part and crystalline dextrose and (be abbreviated as below " CDX ".) 0.2 part, prepare sugary tetra-sodium and be the reductive agent aqueous solution (following, 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 240 parts, water, 60 parts, acrylic rubber matter polymkeric substance (a1-6), KOH0.05 part and SSF1.5 part into.On one side stirring system in, on one side under nitrogen gas stream reaction system heated, thereafter.In the time that internal temperature reaches 60 DEG C, by the total amount supplied reactor of the DX aqueous solution (I).,, through 2 hours continuous adding monomer mixtures (VI) and CHP0.25 part, start polymerization thereafter.During this time, the temperature of reaction system is remained on to 60 DEG C.After the interpolation of whole liquids finishes, internal temperature is warming up to 70 DEG C, further within 1 hour, makes after its slaking in synthermal lower maintenance, finish polyreaction.Thus, obtain containing the latex by acrylic rubber matter enhancing by polymer graft resin and the rubber reinforced resin (S-6) that graftomer does not form.
Then, in this latex, add peptizer, rubber reinforced resin (S-6) is solidified., wash and be dried, reclaim rubber reinforced resin (S-6) thereafter.Table 2 illustrates percentage of grafting and the limiting viscosity of graftomer not.
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) shown in table 2～(a1-11), substitute monomer mixture and use the monomer mixture of the composition shown in table 2, in addition, similarly obtain rubber reinforced resin (S-7)～(S-11) with synthesis example 2-1.The limiting viscosity of the percentage of grafting of each resin and not graftomer is recorded in table 2 simultaneously.
[table 2]
Table 2
Synthesizing of the rubber reinforced resin that 2-4. contains compounded rubber enhancing graft resin
The manufacture method of the rubber reinforced resin [T] that has used the compounded rubber (b1-1) obtaining in above-mentioned synthesis example 2-1 then, is shown.
Synthesis example 2-12
The latex that makes to contain 75 parts of the compounded rubbers (b1-1) that obtain in synthesis example 1-12 is 75 DEG C., on one side stir latex, in this latex, dripped through 20 minutes the mixed solution being formed by BHP0.07 part and MMA12.5 part on one side, carry out polymerization on one side, after dropping finishes, this state is maintained to 30 minutes thereafter.
Then, at 75 DEG C, maintain reaction system on one side, dripped by BHP0.07 part, 9.5 parts of vinylbenzene and 3.0 portions of mixed solutions that form of vinyl cyanide through 25 minutes on one side, carry out polymerization on one side.After dropping finishes, by reaction system under agitation, at 75 DEG C, maintain 1 hour, finish polymerization.Thus, obtain containing the latex that is strengthened graft resin and the rubber reinforced resin (T-1) that graftomer does not form by compounded rubber.
Then, in this latex, add peptizer, rubber reinforced resin (T-1) is solidified., wash and be dried, reclaim rubber reinforced resin (T-1) thereafter.Percentage of grafting is 28%, and the limiting viscosity of graftomer (in methyl ethyl ketone, 30 DEG C) is not 0.35dl/g.
The form of the rubber reinforced resin (T-1) using in the time manufacturing composition in addition, is as described below.; on one side above-mentioned latex is used to spray drying unit, sprays into fine droplet shape with pressure nozzle formula; on one side from supplying with Japanese AEROSIL society hydrophobic silica processed " R-972 " (trade(brand)name) in the mode of the ratio with respect to 100 parts as 0.05 part of rubber reinforced resins (T-1) near hot-wind inlet; be dried (180 DEG C of hot-wind inlet temperature) on one side, obtain the powder being formed by rubber reinforced resin (T-1) and silicon-dioxide.While manufacturing 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)
Use " 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 methyl ethyl ketone, 30 DEG C) is 0.26dl/g, and second-order transition temperature is 170 DEG C.
(ii) vinylbenzene N-phenylmaleimide acrylonitrile copolymer (U-2)
Use " 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 methyl ethyl ketone, 30 DEG C) is 0.27dl/g, and second-order transition temperature is 167 DEG C.
(iii) vinylbenzene N-phenylmaleimide acrylonitrile copolymer (U-3)
Use " 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 DEG C.
(iv) styrene acrylonitrile copolymer (V-1)
For the polymkeric substance being 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, prepare monomer mixture (VIII).
In addition, in 10 parts, water, dissolve EDTA0.1 part, FES0.005 part and NFS0.2 part, prepare the reductive agent aqueous solution and (be abbreviated as below " the SFS aqueous solution (IV) ".)。
And dissolved hydrogen peroxidation diisopropyl benzene (is abbreviated as " IHP " below in 100 parts, water.) 0.25 part, prepare the polymerization starter aqueous solution and (be abbreviated as below " 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 200 parts, water and SDBS2 part into.On one side stirring system in, on one side under nitrogen gas stream reaction system heated, thereafter.In the time that internal temperature reaches 60 DEG C, all through 4 hours continuous adding monomer mixture (VIII) the total amount of total amount, the SFS aqueous solution (IV) and 80% point of the CAT aqueous solution (IV) and start polymerization.The temperature of reaction system is warming up to 70 DEG C in the time that polymerization starts, and thereafter, keeps synthermal.
After beginning polymerization, after 4 hours, 20% point of the residue of the CAT aqueous solution (IV) is supplied to reactor.And, reaction system is kept at 70 DEG C after 1 hour, finish polyreaction.Thus, obtain the latex that contains styrene acrylonitrile copolymer (V-1).
, in this latex add magnesium sulfate (peptizer), styrene acrylonitrile copolymer (V-1) is solidified thereafter.Then, wash and be dried, reclaim the powder being formed by styrene acrylonitrile copolymer (V-1).Limiting viscosity (in methyl ethyl ketone, 30 DEG C) is 0.42dl/g.
2-6. additive
Use following antioxidant.
(1)F-1
Use octadecyl-3-(3,5-, bis--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-, bis--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. thermoplastic resin composition's manufacture and evaluation for lampshade
Embodiment 1～8 and comparative example 1～15
With the mixing ratio of recording in table 3～table 7, raw material [S], [T], [U] and [V] and antioxidant are dropped in Henschel mixer, mix., use toshiba machine society processed twin screw extruder " TEM-50A " (model name), at 220 DEG C～280 DEG C 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 to table 3～table 7 simultaneously.In addition, in table 3～table 7, record composition of the present invention [A], [B] being calculated by material composition, the ratio of [C] and [D].
[table 3]
Table 3
Note: the numerical value of the composition on " thermoplastic resin composition's formation " hurdle is the value when total of [A], [B], [C] and [D] is made as to 100%.
[table 4]
Table 4
Note: the numerical value of the composition on " thermoplastic resin composition's formation " hurdle is the value when total of [A], [B], [C] and [D] is made as to 100%.
[table 5]
Table 5
Note: the numerical value of the composition on " thermoplastic resin composition's formation " hurdle is the value when total of [A], [B], [C] and [D] is made as to 100%.
[table 6]
Table 6
Note: the numerical value of the composition on " thermoplastic resin composition's formation " hurdle is the value when total of [A], [B], [C] and [D] is set as to 100%.
[table 7]
Table 7
Note: the numerical value of the composition on " thermoplastic resin composition's formation " hurdle is the value when total of [A], [B], [C] and [D] is made as to 100%.
Learn following situation by the result shown in table 3～table 7.
Comparative example 1 is not containing the example of composition of the present invention [B], shock resistance and to vibrate deposited property poor.
Comparative example 2 is not 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 and thinks the mixing bad pit causing (disperseing bad) on the surface of injection-molded article, therefore, does not evaluate 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 and think the mixing bad pit causing (disperseing bad) on the surface of injection-molded article, therefore, do not evaluate thereafter.
Comparative example 6 is not 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, appearance, vibrate deposited property and bright property 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, appearance, vibrate deposited property and bright property 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, appearance, vibrate deposited property and bright property 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, appearance, vibrate deposited property and bright property 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, appearance, vibrate deposited property and bright property 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, appearance, vibrate deposited property and bright property poor.
On the other hand, embodiment 1～8 is the example of composition contained in the present invention, shock resistance, thermotolerance, appearance, vibrates the balance excellence of deposited property and bright property.
The composition that uses embodiment 1,2 and 5, carries out the evaluation of the deposited property of hot plate (wire drawing).
The black combination that will be used for the evaluation of the appearance of above-mentioned (7) is supplied with Jing Resin Industry society electric injection moulding machine processed " エ Le ジ ェ Network ト NEX30 " (trade(brand)name), carry out injection molding (220 DEG C～260 DEG C of resin temperatures), obtain the tabular test film of 60mm × 30mm × 3mm.
This test film is carried out under the condition of 23 DEG C of temperature, relative humidity 50% to 3 hours status adjustment, thereafter, use the deposited trier of hot-plate test sheet (イ ダ makes society of institute system), under the following conditions by test film by being pressed on hot plate, the wire drawing of visual observation during from hot plate separation test sheet, result does not produce wire drawing.
< test conditions >
The possibility of industrial application
Lampshade of the present invention is suitable for the formation of the lampshade that forms the lamps apparatus for vehicle such as headlight, taillight, stop light with thermoplastic resin composition.
The explanation of Reference numeral
11: resin lens portion (lamp lens)
12: resin cover portion (lampshade)

Claims (8)

1. lampshade, with thermoplastic resin composition, is characterized in that, contains:
[A] at gel content is more than 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 under 1.1 the existence of acrylic rubber matter polymkeric substance (a1), the acrylic rubber matter enhancing by polymer graft resin that the ethene base system monomer polymerization that contains aromatic ethenyl compound and vinyl cyanide based compound is obtained
[B] contain organo-siloxane be rubber and have from the homopolymer of structural unit of (methyl) alkyl acrylate or the existence of the compounded rubber of copolymer rubber (b1) under, the second-order transition temperature that contains homopolymer is exceeded 0 DEG C (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 the maleimide based copolymer of 10～70 quality % from the structural unit of maleimide amine compound with respect to entire infrastructure unit, and
Optional [D] contains from the structural unit from aromatic ethenyl compound, from least 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, and do not contain the polymkeric substance from the structural unit of maleimide amine compound;
In the case of being that rubber polymer strengthens the total that graft resin [A], above-mentioned compounded rubber strengthen graft resin [B], above-mentioned maleimide based copolymer [C] and above-mentioned polymkeric substance [D] and is made as 100 quality % by aforesaid propylene acid, aforesaid propylene acid is 8～35 quality % that add up to of the content of rubber polymer (a1) and the content of above-mentioned compounded rubber (b1), and
Being made as 100 quality % in the total that is the rubber polymer structural unit that strengthens graft resin [A] by forming aforesaid propylene acid, form structural unit that above-mentioned compounded rubber strengthens graft resin [B], form the structural unit of above-mentioned maleimide based copolymer [C] and form 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 thermoplastic resin composition, wherein, aforesaid propylene acid is that containing of rubber polymer (a1) and above-mentioned compounded rubber (b1) is proportional, in the case of both totals are made as 100 quality %, be respectively 10～95 quality % and 5～90 quality %.
3. the lampshade described in claim 1 or 2 is used thermoplastic resin composition, wherein, aforesaid propylene acid is that rubber polymer (a1) is the polymkeric substance obtaining by carrying out successively the 1st polymerization process and the 2nd polymerization process, described the 1st polymerization process is: under the existence of alkylsulfonate and/or alkyl sulfuric ester salt, by by (methyl) acrylic acid alkyl ester compound (m1-1) with can carry out polymerization in aqueous medium with the monomer (m1) that other compounds (m1-2) of this (methyl) acrylic acid alkyl ester compound (m1-1) copolymerization form, form the operation of the 1st polymkeric substance, described the 2nd polymerization process is: under the existence of above-mentioned the 1st polymkeric substance, under the existence of alkylsulfonate and/or alkyl sulfuric ester salt or under non-existence, will be by (methyl) acrylic acid alkyl ester compound (m2-1), there is the polymerizable unsaturated compound (m2-2) of more than 2 carbon-to-carbon double bond and the operation that can carry out polymerization in aqueous medium with the monomer (m2) that other compounds (m2-3) of this (methyl) acrylic acid alkyl ester compound (m2-1) and this polymerizable unsaturated compound (m2-2) copolymerization form,
In above-mentioned the 1st polymerization process, the ratio of the usage quantity of above-mentioned (methyl) acrylic acid alkyl ester compound (m1-1) and above-mentioned other compounds (m1-2), when both totals are designated as to 100 quality %, is respectively 50～100 quality % and 0～50 quality %,
In above-mentioned the 2nd polymerization process, the ratio of the usage quantity of above-mentioned (methyl) acrylic acid alkyl ester compound (m2-1), above-mentioned polymerizable unsaturated compound (m2-2) and above-mentioned other compounds (m2-3), when their total is designated as to 100 quality %, be respectively 50～99.99 quality %, 0.01～5 quality % and 0～49.99 quality %
The ratio of above-mentioned monomer (m1) and usage quantity (m2), in the case of both totals are made as 100 quality %, is respectively 1～50 quality % and 50～99 quality %.
4. lampshade as claimed in claim 1 or 2 is used thermoplastic resin composition, and it is that the raw material that comprises following component is obtained by mixing:
[S] contains in aforesaid propylene acid is under the existence of rubber polymer (a1), the rubber reinforced resin of the acrylic rubber matter enhancing by polymer graft resin that the ethene base system monomer that does not contain maleimide amine compound, comprises aromatic ethenyl compound and vinyl cyanide based compound is carried out to polymerization and obtain
[T] contains under the existence of above-mentioned compounded rubber (b1), (methyl) acrylic acid alkyl ester compound that the second-order transition temperature of homopolymer is exceeded to 0 DEG C is carried out polymerization, then the compounded rubber that the ethene base system monomer that does not contain maleimide amine compound, comprises aromatic ethenyl compound and vinyl cyanide based compound is carried out to polymerization and obtain strengthens the rubber reinforced resin of graft resin, and
[U] contains the maleimide based copolymer of 10～70 quality % from the structural unit of maleimide amine compound with respect to entire infrastructure unit.
5. lampshade as claimed in claim 1 or 2 is with thermoplastic resin composition, wherein, above-mentioned lampshade be impregnated in acetone with thermoplastic resin composition and the limiting viscosity of the acetone soluble polymer obtaining is 0.2～1.0dl/g.
6. lampshade as claimed in claim 1 or 2 is used thermoplastic resin composition, and it is for forming the molding material of the products formed of evaporation layer on its surface by direct evaporation.
7. lampshade as claimed in claim 1 or 2 is used thermoplastic resin composition, and it is for being suitable for the molding material of the products formed that vibrates deposited method.
8. products formed, is characterized in that, contains the lampshade described in any one in claim 1～7 and uses thermoplastic resin composition.
CN201180026362.2A 2010-06-24 2011-06-21 Thermoplastic resin composition for lamp housings, and molded articles Expired - Fee Related CN102918103B (en)

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