CN1922264A - Vinyl chloride resin composition - Google Patents
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- CN1922264A CN1922264A CN 200580005715 CN200580005715A CN1922264A CN 1922264 A CN1922264 A CN 1922264A CN 200580005715 CN200580005715 CN 200580005715 CN 200580005715 A CN200580005715 A CN 200580005715A CN 1922264 A CN1922264 A CN 1922264A
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Abstract
A vinyl chloride resin composition which, even when various compounding ingredients are not added thereto in a large amount, shows excellent melt flow characteristics without lowering the softening temperature and mechanical strength/properties of the molding to be obtained therefrom; and a molding formed from the composition. The vinyl chloride resin composition is characterized by being obtained by adding to a vinyl chloride resin a vinyl chloride copolymer resin obtained by copolymerizing a vinyl monomer with a macromonomer having a main chain comprising a polymer of an ethylenically unsaturated monomer having a double bond.
Description
Technical field
The present invention relates to vinyl chloride resin composition and used the formed body of said composition.More particularly, relate under the situation that the softening temperature that does not make formed body and physical strength rerum natura reduce the vinyl chloride resin composition of melt flow characteristics excellence and used the formed body of said composition.More particularly, the present invention relates to: when the vinyl chloride resin that has the mean polymerisation degree of the scope of using in the common rolling processing purposes or a molecular-weight average in use carries out rolling processing, be used to obtain to suppress simultaneously air marks (air mark) that the moulding surface produces and ripple (flow mark), condition of surface excellence the rolling processing formed body vinyl chloride resin composition and used the rolling processing vinyl chloride resin formed body of said composition; And the vinyl chloride resin that uses mean polymerisation degree with normally used scope in the injection molded article purposes or molecular-weight average is when carrying out injection molding, is used to obtain the intensity rerum natura and not have to reduce, the vinyl chloride resin composition of the injection molded article of the mobile excellence during forming process and used the injection vinyl chloride resin formed body of said composition; And to formed body, particularly pipe that use has a vinyl chloride resin extrusion moulding of the mean polymerisation degree of normally used scope in extrusion moulding body and function way or molecular-weight average wait require shock strength and as the useful hard vinyl chloride based resin composition of the hard extrusion moulding body of the fracture toughness property intensity of the new long durability pointer that is used for high-qualityization and used said composition extrude the hard vinyl chloride resin molded body.
Background technology
It is general in various formed bodys that vinyl chloride resin effectively utilizes its characteristic, but have heat decomposition temperature near processing temperature, and be difficult to manifest the fully flowability of satisfaction degree and the variety of issue of physical strength rerum natura relevant processing such as (for example resistance to impact shock, tensile strength, fracture toughness property intensity etc.).In order to overcome this problem, known for example have other monomers of copolymerization on the vinyl chloride monomer or in vinyl chloride resin the method for plastic binder or other resin-like things.But, these methods have can not solve the shortcoming of processing the problem that relates under the situation of the physicochemical property of keeping vinyl chloride resin inherent excellence, for example when vinyl chloride monomer and other monomer copolymerizations or interpolation softening agent, the softening temperature of the formed body that obtains reduces, bad mechanical strength, and mix other resin-like things in most cases, the viscosity that dissolves of resin compound is reduced, thereby improve the processibility on apparent, but because bad with the consistency of vinyl chloride resin, therefore the mechanical properties of the formed body that obtains and the transparency are poor.
On the other hand, in order to improve resistance to impact shock, there is document to disclose for example in vinyl chloride resin, to add MBS (being designated hereinafter simply as the MBS resin) or chlorinatedpolyethylene (being designated hereinafter simply as CPE) method (patent documentation 1) as the shock resistance toughener as one of physical strength rerum natura.But, when in vinyl chloride resin, cooperating these tougheners, in order to give its sufficient mechanical, must cooperate a large amount of tougheners, need cost, but also the flowability can produce forming process the time can not get improving, for example the motor load of forcing machine such as increases at the problem of the aspect of creating conditions.In addition, for under the situation of the mechanical characteristics that does not reduce the vinyl chloride resin formed body and the transparency, gelation or improve flowability and secondary workability when promoting forming process, the method (patent documentation 2) that has document to propose for example will to be the multipolymer of main component to cooperate as the processibility modifying agent with the methyl methacrylate.But, though this method promotes gelation under the situation that does not reduce the characteristic that vinyl chloride resin has, can access the formed body of the transparency and secondary workability and air marks excellence, but the fatal shortcoming that exists is, the calendered sheet surface produces ripple when rolling processing, and the commodity value of formed body is reduced.And in order to improve this ripple, having document to propose will be the method (patent documentation 3) that the low multipolymer of the main component and the polymerization degree cooperates as the processibility modifying agent with the methacrylic ester beyond the methyl methacrylate for example.But, though this method has been improved ripple, also sacrificed simultaneously the preferred effect that air marks reduces and secondary workability improves of utilizing patent documentation 2 described methods etc. to give, also the result with the commodity value reduction that causes formed body is relevant for these.In recent years, market is more and more higher to the requirement of quality, as long as can also can reduce air marks in the generation that suppresses ripple, then becomes industrial very useful technology.
Wherein, so-called air marks, the air that is involved in when being meant melting mixing in the molten resin does not have Ex-all, and its vestige becomes the apperance of point-like or muscle shape and remains in the part on formed body surface.In addition, so-called ripple, a part that is meant the molten resin mass that produces in the roller gap because by the flow velocity of front and back and the variation of resin temperature etc., becomes the apperance of muscle shape or striated and remains in the part on formed body surface by this gap the time.
And, method as the desired characteristic of improvement under the situation of mismatching multiple a large amount of toughener and additive, there is document to disclose following method: for example in order to improve resistance to impact shock and resistance to fatigue, on the acrylic copolymer that adopts existing known general emulsion polymerization to obtain, make vinyl monomer graft copolymerization, with the resin that obtains thus as hard vinyl chloride pipe (patent documentation 4).But in the method, the vinyl chloride copolymer resin for obtaining helps to improve resistance to impact shock though disclose, relevant fracture toughness property intensity to improve effect indeterminate.
Patent documentation 1: the spy opens flat 9-278964 communique
Patent documentation 2: special public clear 53-2898 communique
Patent documentation 3: the spy opens flat 1-247409 communique
Patent documentation 4: the spy opens the 2003-148660 communique
Summary of the invention
The object of the present invention is to provide under the situation that the softening temperature that does not make formed body and physical strength rerum natura reduce the vinyl chloride resin composition of melt flow characteristics excellence and used the vinyl chloride resin formed body of said composition.In addition, the object of the present invention is to provide and give air marks and ripple all is inhibited, the vinyl chloride resin composition of the calendering machine-shaping bodies such as sheet material of condition of surface excellence and used the rolling processing vinyl chloride resin formed body of said composition.And, the object of the present invention is to provide under the situation of mismatching multiple a large amount of additive good fluidity during forming process and intensity rerum natura undiminished injection molding body and function vinyl chloride resin composition and used the injection vinyl chloride resin formed body of said composition.And, the object of the present invention is to provide under the situation of mismatching multiple a large amount of toughener, can give high impact and high-fracture toughness intensity extrude processing with the hard vinyl chloride based resin composition and used said composition extrude the hard vinyl chloride resin molded body.
Present inventors study without single devotion, found that: the vinyl chloride resin composition that contains the vinyl chloride copolymer resin by use, described vinyl chloride copolymer resin is with vinyl monomer and macromonomer copolymerization and obtain, described macromonomer has the polymkeric substance that is made of the ethylenically unsaturated monomers that contains two keys on main chain, can finish above-mentioned problem, finish the present invention.
That is, the present invention relates to:
(1) vinyl chloride resin composition, it is characterized in that: the vinyl chloride copolymer resin is added in the vinyl chloride resin, described vinyl chloride copolymer resin obtains by making vinyl monomer and macromonomer copolymerization, and described macromonomer has the polymkeric substance that is made of the ethylenically unsaturated monomers that contains two keys on main chain.
(2) vinyl chloride resin composition is characterized in that: with vinyl chloride resin 100 weight parts is benchmark, and the content of this macromonomer composition is 0.1～5 weight part.
(3) vinyl chloride resin composition is characterized in that: in this vinyl chloride copolymer resin, this macromonomer composition accounts for 3～50 weight %.
(4) formed body, it is formed by above-mentioned described vinyl chloride resin composition.
(5) formed body is characterized in that: adopt rolling processing to make its moulding.
(6) formed body is characterized in that: adopt injection molding to become to make its type.
(7) formed body is characterized in that: adopt its type that makes that is extrusion-molded into.
According to vinyl chloride resin composition of the present invention, can obtain the vinyl chloride resin formed body that softening temperature and physical strength rerum natura do not have reduction and melt flow characteristics excellence.In addition, according to vinyl chloride resin composition of the present invention, can obtain the rolling processing vinyl chloride resin formed body that air marks and ripple all are inhibited.And according to vinyl chloride resin composition of the present invention, good fluidity in the time of can obtaining forming process and intensity rerum natura do not have injection vinyl chloride resin formed bodys such as reduction, joint and valve goods.And, according to vinyl chloride resin composition of the present invention, can obtain under the situation of mismatching multiple a large amount of toughener and additive, pipe with high impact and high-fracture toughness intensity etc. is extruded the hard vinyl chloride resin molded body.
Embodiment
Vinyl chloride resin composition of the present invention is characterised in that: the vinyl chloride copolymer resin that the macromonomer copolymerization that has the polymkeric substance that is made of the ethylenically unsaturated monomers that contains two keys on vinyl monomer and the main chain is obtained adds in the vinyl chloride resin, the said composition forming process is become the method for various formed bodys, be not particularly limited, can enumerate the shaping operation method of common vinyl chloride resin such as for example rolling processing method, injection moulding, extrusion process method, blow molding method, extrusion forming method, vacuum forming etc.In the present invention, the mean polymerisation degree or the molecular-weight average of the vinyl chloride resin that in these various forming process, uses, so long as can obtain the scope of effect of the present invention, just be not particularly limited, same with the vinyl chloride resin of common manufacturing and use, the K value of measuring according to JIS K 7367-2 is 50～95 scope.At this, the so-called rolling processing of using vinyl chloride resin, be meant that in warming mill dropping into resin combination etc. carries out melting mixing and calendering, the method for processing forming of cooling curing slabbing, as employed vinyl chloride resin, the mean polymerisation degree that has the K value of measuring according to JIS K 7367-2 and be 58～68 scopes is comparatively suitable.In addition, the so-called injection molding processing method of using vinyl chloride resin, be meant and utilize screw rod that resin combination etc. is sent in the heating cylinder, utilize the heat of barrel and the shearing that screw rod produces, it is flowed heating and meltings such as said composition, injections such as this molten resin composition are injected in the mould, cooling curing obtains the shaping operation method of formed body, as employed vinyl chloride resin, the mean polymerisation degree that has the K value of measuring according to JIS K 7367-2 and be 55～61 scopes is comparatively suitable.In addition, the so-called extrusion process method that uses vinyl chloride resin, be meant and utilize screw rod that resin combination etc. is sent in the heating cylinder, utilize the heat of barrel and the shearing that screw rod produces, it is flowed heating and meltings such as said composition, make its mould figuration that passes through front end, cooling curings such as its water are obtained the shaping operation method of formed body, as employed vinyl chloride resin, the mean polymerisation degree that has the K value of measuring according to JIS K 7367-2 and be 60～73 scope is comparatively suitable.In addition,,, all be not particularly limited, be generally the scope of 50～300 μ m no matter be any shaping operation method as median size.
Should illustrate, so-called " the vinyl chloride copolymer resin is added in the vinyl chloride resin ", be to instigate two kinds of resins after each auto-polymerization, to mix, as its method, so long as can obtain the scope of effect of the present invention, just be not particularly limited the powder body blended method that can exemplify the material blended method of the latex shape that makes after the polymerization and/or paste-like, latex and/or slurry drying are obtained, with the material of latex shape or paste-like and powder body blended method etc.
As the vinyl monomer that constitutes the vinyl chloride copolymer resin that uses among the present invention, be not particularly limited, can use and be selected from for example vinyl chloride monomer, vinylidene chloride monomer, vinyl acetate monomer or these mixture, or in addition can with main polymer chain after these copolymerization, the preferred polymeric on do not have the monomer of reactive functional groups, the mixture of one or more of alpha-olefines such as ethene, propylene for example.When using two or more mixtures, preferably the containing ratio of vinyl chloride monomer accounts for more than or equal to 50 weight %, is preferably greater than especially and equals 70 weight % in whole vinyl monomers.Wherein,, preferably only use any of vinyl chloride monomer or vinylidene chloride monomer, the further preferred vinyl chloride monomer that uses from the considerations such as rerum natura of the copolymer resins that obtains.
Common so-called macromonomer is meant that the end of polymkeric substance has the oligomer molecules of reactive functional groups.The macromonomer that has the polymkeric substance that constitutes by the ethylenically unsaturated monomers that contains two keys on the main chain that uses among the present invention, utilize the radical polymerization manufacturing to form, as reactive functional groups, has the individual group that is selected from allyl group, vinyl silyl, vinyl ether group, bicyclic pentadiene, following general formula (1) of per at least 1 molecule 1 with polymerizability carbon-to-carbon double bond in molecular end.
From considering to have the preferred especially following general formula of group (1) of polymerizability carbon-to-carbon double bond with the reactive good aspect of vinyl monomer:
-OC(O)C(R)＝CH
2 (1)
The group of expression.
In the formula, the concrete example of R is not particularly limited, preferably from for example-H ,-CH
3,-CH
2CH
3,-(CH
2)
nCH
3(n represents 2～19 integer) ,-C
6H
5,-CH
2OH ,-group selected among the CN, further preferred-H ,-CH
3
Polymkeric substance as the ethylenically unsaturated monomers by containing two keys of the main chain of the macromonomer that uses among the present invention constitutes utilizes the incompatible manufacturing of radical polymerization.Radical polymerization can be categorized as " general radical polymerization ", and it uses azo compound, superoxide etc. as polymerization starter, makes simply to have monomer and the vinyl monomer copolymerization that specific official is subjected to group; " controlled free radical polymerization method ", it can wait in check position to introduce specific functional group endways.
Because only will having particular functional group's monomer probability ground, " general radical polymerization " introduce in the polymkeric substance, therefore when wanting to obtain the high polymkeric substance of functionalized rate, and must this quite a large amount of monomer of use.In addition, owing to be radical polymerization, so molecular weight distribution is wide, is difficult to obtain the low polymkeric substance of viscosity.
" controlled free radical polymerization method " can also be categorized as " chain-transfer agent method ", and it carries out polymerization by the chain-transfer agent that use has the particular functional group, can be had the vinylic polymers of functional group endways; " living radical polymerization ", it does not cause that by the aggregation growth end termination reaction grows, and can be met the polymkeric substance of the molecular weight of design substantially.
" chain-transfer agent method " can obtain the high polymkeric substance of functionalized rate, but need have particular functional group's chain-transfer agent with respect to initiator.In addition, same with above-mentioned " general radical polymerization ", owing to be radical polymerization, so molecular weight distribution is wide, is difficult to obtain the low polymkeric substance of viscosity.
Different with these polymerizations, " living radical polymerization " discloses as described in the WO99/65963 communique as the related world of the applicant's oneself invention, because polymerization velocity is fast, coupling between the free radical etc. causes termination reaction easily, make it become unmanageable radical polymerization, but be difficult to produce termination reaction, obtaining narrow molecular weight distribution, when for example the ratio (Mw/Mn) of weight-average molecular weight Mw and number-average molecular weight Mn is about 1.1～1.5 polymkeric substance, can freely control molecular weight by the charge ratio of monomer and initiator.
Thereby, " living radical polymerization " can access the polymkeric substance that molecular weight distribution is narrow, viscosity is low, and because the almost optional position that the monomer with particular functional group can be introduced polymkeric substance, therefore in the present invention, as the manufacture method of the vinylic polymers with above-mentioned particular functional group, it is preferred polymerization.
In " living radical polymerization "; with Organohalogen compounds or halogenation sulfonyl compound etc. is initiator; with the transition metal complex is that catalyzer makes vinyl monomer polymeric " Transfer Radical Polymerization " (Atom Transfer Radical Polymerization:ATRP); because not only have the feature of above-mentioned " living radical polymerization "; and has halogen that is beneficial to functional group's conversion reaction etc. endways; initiator and catalyst design degree of freedom are big, therefore as the manufacture method of the vinylic polymers with particular functional group and more preferably.As this Transfer Radical Polymerization, for example can enumerate Matyjaszewski etc., J.Am.Chem.Soc.1995,117 volumes, 5614 pages etc.
Manufacture method as the macromonomer that constitutes the vinyl chloride copolymer resin that uses among the present invention, use which kind of method in these, be not particularly limited, usually utilize the controlled free radical polymerization method, further calm aspect such as easy to control is considered, the preferred living radical polymerization that uses, particularly Transfer Radical Polymerization most preferably.
In addition, the polymkeric substance that the ethylenically unsaturated monomers by containing two keys that has as the main chain of the macromonomer that constitutes the vinyl chloride copolymer resin that uses among the present invention constitutes, be not particularly limited, the ethylenically unsaturated monomers that contains two keys as constituting this polymkeric substance can use various monomers.Can enumerate for example (methyl) vinylformic acid, (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 n-pentyl ester, the just own ester of (methyl) vinylformic acid, (methyl) cyclohexyl acrylate, the positive heptyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid n-octyl, (methyl) ethyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) lauryl acrylate, (methyl) phenyl acrylate, (methyl) CA, (methyl) benzyl acrylate, (methyl) vinylformic acid-2-methoxyl group ethyl ester, (methyl) vinylformic acid-3-methoxyl group butyl ester, (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-2-hydroxy propyl ester, (methyl) stearyl acrylate ester, (methyl) glycidyl acrylate, (methyl) vinylformic acid-2-amino ethyl ester, γ-(methacryloxypropyl) Trimethoxy silane, (methyl) acrylic acid ethylene oxide adduct, (methyl) vinylformic acid trifluoromethyl methyl esters, (methyl) vinylformic acid 2-trifluoromethyl ethyl ester, (methyl) vinylformic acid 2-perfluor diethyl acetamidomalonate, (methyl) vinylformic acid 2-perfluor ethyl-2-perfluoro butyl ethyl ester, (methyl) vinylformic acid 2-perfluor ethyl ester, (methyl) vinylformic acid perfluor methyl esters, (methyl) vinylformic acid two perfluoro-methyl methyl esters, (methyl) vinylformic acid 2-perfluoro-methyl-2-perfluor ethyl methyl esters, (methyl) vinylformic acid 2-perfluoro hexyl ethyl ester, (methyl) vinylformic acid 2-perfluor decyl ethyl ester, (methyl) acrylic monomers such as (methyl) vinylformic acid 2-perfluor hexadecyl ethyl ester; Styrene monomers such as vinylbenzene, Vinyl toluene, alpha-methyl styrene, chloro-styrene, styrene sulfonic acid and salt thereof; Perfluoro-ethylene, perfluoro propylene, vinylidene etc. contain the vinyl monomer of fluorine; Vinyltrimethoxy silane, vinyltriethoxysilane etc. contain the vinyl monomer of silicon; One alkyl ester and the dialkyl of maleic anhydride, toxilic acid, toxilic acid; One alkyl ester and the dialkyl of fumaric acid, fumaric acid; Maleimide monomers such as maleimide, methyl maleimide, ethyl maleimide, propyl group maleimide, butyl maleimide, hexyl maleimide, octyl group maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl maleimide; Vinyl cyanide, methacrylonitrile etc. contain the vinyl monomer of itrile group; Acrylamide, Methacrylamide etc. contain the vinyl monomer of amide group; Vinyl esters such as vinyl-acetic ester, propionate, trimethylacetic acid vinyl acetate, vinyl benzoate, vinyl laurate; Olefines such as ethene, propylene; Divinyl, isoprene equiconjugate dienes; Chlorallylene, vinyl carbinol etc.These can use separately, also can be with two or more copolymerization.Wherein, from the considerations such as rerum natura of resultant, optimization styrene class monomer or (methyl) acrylic monomer.More preferably acrylate monomer or methacrylate monomer, further preferred acrylate monomer, most preferably butyl acrylate.In the present invention, at this moment the material that can use these preferred monomers and other monomer copolymerizations to form, preferably comprises weight ratio more than or equal to these preferred monomers of 40%.Wherein, what is called is " (methyl) vinylformic acid " for example, is meant acrylic or methacrylic acid.
The macromonomer of the formation vinyl chloride copolymer resin that uses among the present invention is characterised in that: have the polymkeric substance that is made of these ethylenically unsaturated monomers that contains two keys on the main chain, and molecular end has the individual reactive functional groups of per at least 1 molecule 1.
And can only using with the macromonomer of vinyl monomer copolymerization of the formation vinyl chloride copolymer resin that uses among the present invention is a kind of, also can use the different macromonomer of ethylenically unsaturated monomers of two or more formations simultaneously.
In the whole vinyl chloride copolymer resins that use among the present invention, has the branch rate that the macromonomer composition of the polymkeric substance that is made of the ethylenically unsaturated monomers that contains two keys is occupied on the main chain, so long as obtain the scope of effect of the present invention, just be not particularly limited, be preferably 3～50 weight %.If having the branch rate of the macromonomer composition of the polymkeric substance that is made of the ethylenically unsaturated monomers that contains two keys on the main chain is the scope of 3～50 weight %, then can expect following effect: copolyreaction is stable, and the vinyl chloride copolymer resin that obtains becomes the powder body, the maneuverable degree of freedom increase that makes working method simultaneously.In addition, by the vinyl chloride copolymer resin that use obtains, can obtain under the situation of softening temperature that does not make formed body and the reduction of physical strength rerum natura the vinyl chloride resin composition of melt flow characteristics excellence.Particularly utilize rolling processing, injection molding, hard to extrude the various shaping operation methods of processing, when obtaining formed body by vinyl chloride copolymer resin combination of the present invention, the shared branch rate of macromonomer composition in the whole vinyl chloride copolymer resins that use, so long as obtain the scope of effect of the present invention, just be not particularly limited, be preferably 5～50 weight %.If the branch rate of macromonomer composition is the scope of 5～50 weight %, the vinyl chloride copolymer resin that obtains by use then, can obtain the rolling processing vinyl chloride resin formed body that air marks and ripple all are inhibited, in addition, injection such as the good fluidity in the time of can obtaining forming process and undiminished joint of intensity rerum natura and valve goods vinyl chloride resin formed body, in addition, under the situation that does not cooperate multiple a large amount of toughener and additive, pipe that can obtain having high impact and high-fracture toughness intensity etc. is extruded the hard vinyl chloride resin molded body.
The mean polymerisation degree or the molecular-weight average of the vinyl chloride copolymer resin that uses among the present invention, so long as obtain the scope of effect of the present invention, just be not particularly limited, same with the vinyl chloride resin of common manufacturing and use, the K value of measuring according to JIS K 7367-2 is 50～95 scope.In addition, median size is not particularly limited, and is generally the scope of 0.01～500 μ m, is preferably the scope of 0.1～300 μ m, more preferably the scope of 50～300 μ m.As long as median size is the scope of 50～300 μ m, just can provide desired various quality characteristic isostatic starting material.
In the present invention, the vinyl chloride copolymer resin that the macromonomer copolymerization that has the polymkeric substance that is made of the ethylenically unsaturated monomers that contains two keys on vinyl monomer and the main chain is obtained adds in the vinyl chloride resin and uses, with vinyl chloride resin 100 weight parts is benchmark, the content of this macromonomer composition in this vinyl chloride copolymer resin, so long as obtain the scope of effect of the present invention, just be not particularly limited, but preferably add this vinyl chloride copolymer resin, so that it reaches the following scope of 0.1～5 weight part.If with vinyl chloride resin 100 weight parts is benchmark, the content of this macromonomer composition in this vinyl chloride copolymer resin is the scope of 0.1～5 weight part, and desired various quality characteristic isostatic starting material just can be provided.Wherein, when vinyl chloride copolymer resin of the present invention is used for the injection molding purposes, with vinyl chloride resin 100 weight parts is benchmark, the content of this macromonomer composition in this vinyl chloride copolymer resin is so long as obtain the scope of effect of the present invention, just be not particularly limited, preferred this vinyl chloride copolymer resin that adds is so that it reaches the scope of 0.1～1 weight part.If with vinyl chloride resin 100 weight parts is benchmark, the content of this macromonomer composition in this vinyl chloride copolymer resin is the scope of 0.1～1 weight part, the intensity rerum natura isostatic starting material of flowability in the time of just can providing forming process and formed body.
Manufacture method for the vinyl chloride copolymer resin that uses among the present invention, be not particularly limited, consider from the simplicity aspect of polymerization control, the preferably copolymerization in aqueous medium, such polymerization process for example has: manufacture method such as suspension polymerization, microsuspension method, emulsion polymerization.Wherein, in order to obtain the vinyl chloride copolymer resin that median size is the scope of 50～300 μ m, preferred suspension polymerization.Adopt such manufacture method, can obtain this vinyl chloride copolymer resin of latex shape or paste-like, as the method that is dried the vinyl chloride copolymer resin that obtains the powder body, be not particularly limited, can enumerate and for example latex be utilized spray-drying process to carry out the exsiccant method, will utilize the desiccating method that flows to carry out the exsiccant method, will utilize the standing and drying method to carry out exsiccant method etc. behind the slurry dewatering behind the slurry dewatering.
In the present invention, the vinyl chloride copolymer resin that the macromonomer copolymerization that has the polymkeric substance that is made of the ethylenically unsaturated monomers that contains two keys on vinyl monomer and the main chain is obtained adds in the vinyl chloride resin and uses, the monomer that constitutes this vinyl chloride resin is to be the monomer of main component with the vinyl chloride monomer, specifically, it is independent vinyl chloride monomer, or contain more than or equal to 50 weight %, particularly more than or equal to 70 weight % vinyl chloride monomers, can with the vinyl chloride monomer copolymerization, there are not the monomer of reactive functional groups and the mixture of vinyl chloride monomer on the main polymer chain after the preferred polymeric.Can for example have with the monomer of vinyl chloride monomer copolymerization: vinyl esters such as vinyl-acetic ester, propionate; Alpha-olefines such as ethene, propylene, IVE; Chloro-alkenes classes such as 1-propenyl chloride, 2-chlorobutylene; (methyl) esters of acrylic acids such as (methyl) methyl acrylate; Maleic anhydride, vinyl cyanide, vinylbenzene, vinylidene chloride etc., these can use separately, also two or more can be used in combination.
Manufacture method for the vinyl chloride resin that uses among the present invention, be not particularly limited, consider from the simplicity aspect of polymerization control, the preferably polymerization in aqueous medium, such polymerization process for example has: manufacture method such as suspension polymerization, microsuspension method, emulsion polymerization.Wherein, same with the vinyl chloride resin that uses in the shaping operation method of the common vinyl chloride resin of for example rolling-molding method, extrusion moulding, injection moulding, blow molding method, extrusion forming method, vacuum forming etc., preferably utilize suspension polymerization manufacturing.Adopt such manufacture method, can obtain this vinyl chloride resin of latex shape or paste-like, as the method that is dried the vinyl chloride resin that obtains the powder body, be not particularly limited, can enumerate and for example latex be utilized spray-drying process to carry out the exsiccant method, will utilize the desiccating method that flows to carry out the exsiccant method, will utilize the standing and drying method to carry out exsiccant method etc. behind the slurry dewatering behind the slurry dewatering.
Wherein, be benchmark with vinyl chloride resin 100 weight parts, have the content of the macromonomer composition of the polymkeric substance that constitutes by the ethylenically unsaturated monomers that contains two keys on the main chain in the vinyl chloride copolymer resin, calculate by following calculating formula (2).
Z＝X×Y÷100 (2)
Z: with vinyl chloride resin 100 weight parts is benchmark, has the content (weight part) of the macromonomer composition of the polymkeric substance that is made of the ethylenically unsaturated monomers that contains two keys on the main chain in the vinyl chloride copolymer resin
X: in the vinyl chloride copolymer resin, have the branch rate (weight %) that the macromonomer composition of the polymkeric substance that is made of the ethylenically unsaturated monomers that contains two keys occupies on the main chain
Y: with respect to vinyl chloride resin 100 weight parts, the interpolation umber (weight part) of vinyl chloride copolymer resin
In the vinyl chloride resin composition of the present invention, with vinyl chloride resin, and the vinyl chloride copolymer resin that obtains of the macromonomer copolymerization of the polymkeric substance that will have on vinyl monomer and the main chain constitutes by the ethylenically unsaturated monomers that contains two keys be neccessary composition, in the scope of not damaging the object of the invention, can suitably cooperate thermo-stabilizer, lubricant, stabilizing additive, processing aid, weighting agent, oxidation inhibitor, photostabilizer, pigment, softening agent etc. as required.
Thermo-stabilizer is not particularly limited, and can use the material of the scope that does not influence the object of the invention.Such thermo-stabilizer for example has: organic tin thermo-stabilizers such as sulfydryl tin methide, sulfydryl dibutyl tin, sulfydryl dioctyl tin, toxilic acid dibutyl tin, dibutyltin maleate polymer, dioctyl tin maleate, dioctyl tin maleate polymkeric substance, dibutyl tin laurate, dibutyl tin laurate polymkeric substance; Plumbous type thermal stabilizing agents such as lead stearate, dibasic lead phosphite, tribasic lead sulfate; Calcium-zinc type thermal stabilizing agent; Barium-zinc type thermal stabilizing agent; Cadmium-barium type thermal stabilizing agents etc., these can use separately, also can 2 kinds or multiple use simultaneously.In addition, its usage quantity also is not particularly limited, do not get final product so long as do not influence the scope of the object of the invention, and be scope preferably during use smaller or equal to 5 weight parts with respect to vinyl chloride resin 100 weight parts.
In addition, lubricant is not particularly limited, and can use the material of the scope that does not influence the object of the invention.Such lubricant for example has: paraffin class lubricant, polyolefin-wax series lubricant agent, stearic acid lubricant, pure series lubricant agent, ester series lubricant agent etc., these can use separately, also can 2 kinds or multiple use simultaneously.In addition, its usage quantity also is not particularly limited, do not get final product so long as do not influence the scope of the object of the invention, and be scope preferably during use smaller or equal to 3 weight parts with respect to vinyl chloride resin 100 weight parts.
In addition, stabilizing additive is not particularly limited, and can use the material of the scope that does not influence the object of the invention.Such stabilizing additive for example has: epoxy soybean oil, epoxidation linseed oil, epoxidation tetrahydrophthalic acid ester, epoxidized polybutadiene, phosphoric acid ester etc., these can use separately, also can be with 2 kinds or multiple use simultaneously.In addition, its usage quantity also is not particularly limited, do not get final product so long as do not influence the scope of the object of the invention, and be scope preferably during use smaller or equal to 3 weight parts with respect to vinyl chloride resin 100 weight parts.
In addition, processing aid is not particularly limited, and can use the material of the scope that does not influence the object of the invention.Such processing aid for example has: n-butyl acrylate/methylmethacrylate copolymer, ethyl acrylate/methylmethacrylate copolymer, ethyl acrylate/methyl methacrylate/acrylic processing aids such as n-BMA multipolymer etc., these can use separately, also can be with 2 kinds or multiple use simultaneously.In addition, its usage quantity also is not particularly limited, do not get final product so long as do not influence the scope of the object of the invention, and be scope preferably during use smaller or equal to 10 weight parts with respect to vinyl chloride resin 100 weight parts.
In addition, weighting agent is not particularly limited, and can use the material of the scope that does not influence the object of the invention.Such weighting agent for example has: lime carbonate, magnesiumcarbonate, Quilonum Retard, kaolin, gypsum, mica, talcum, magnesium hydroxide, Calucium Silicate powder, borax etc., these can use separately, also can be with 2 kinds or multiple use simultaneously.In addition, its usage quantity also is not particularly limited, do not get final product so long as do not influence the scope of the object of the invention, and be scope preferably during use smaller or equal to 1000 weight parts with respect to vinyl chloride resin 100 weight parts.
In addition, oxidation inhibitor is not particularly limited, and can use the material of the scope that does not influence the object of the invention.Such oxidation inhibitor for example has: phenolic antioxidant etc., these can use separately, also can be with 2 kinds or multiple use simultaneously.In addition, its usage quantity also is not particularly limited, do not get final product so long as do not influence the scope of the object of the invention, and be scope preferably during use smaller or equal to 5 weight parts with respect to vinyl chloride resin 100 weight parts.
In addition, photostabilizer is not particularly limited, and can use the material of the scope that does not influence the object of the invention.Such photostabilizer for example has: UV light absorber such as salicylate class, benzophenone, benzotriazole category, cyanoacrylate; Hindered amine light stabilizers etc., these can use separately, also can be with 2 kinds or multiple use simultaneously.In addition, its usage quantity also is not particularly limited, do not get final product so long as do not influence the scope of the object of the invention, and be scope preferably during use smaller or equal to 5 weight parts with respect to vinyl chloride resin 100 weight parts.
In addition, pigment is not particularly limited, and can use the material of the scope that does not influence the object of the invention.Such pigment for example has: pigment dyestuffs such as azo class, phthalocyanines, intellectual circle's class, dyestuff color lake class; Mineral dyes such as oxide-based, chromic acid molybdenum class, sulfide selenide class, yellow prussiate class etc., these can use separately, also can 2 kinds or multiplely use simultaneously.In addition, its usage quantity also is not particularly limited, do not get final product so long as do not influence the scope of the object of the invention, and be scope preferably during use smaller or equal to 5 weight parts with respect to vinyl chloride resin 100 weight parts.
In addition, softening agent is not particularly limited, and can use the material of the scope that does not influence the object of the invention.Such softening agent for example has: phthalic ester plasticizers such as di-2-ethylhexyl phthalate, dinoctyl phthalate, diisononyl phthalate, dibutyl phthalate; Phosphate plasticizer such as tricresyl phosphate (toluene ester), tricresyl phosphate (diformazan phenyl ester), triphenylphosphate; Fatty acid ester plasticisers such as di-2-ethylhexyl adipate, Diisooctyl Sebacate etc., these can use separately, also can be with 2 kinds or multiple use simultaneously.In addition, its usage quantity also is not particularly limited, do not get final product so long as do not influence the scope of the object of the invention, and be scope preferably during use smaller or equal to 100 weight parts with respect to vinyl chloride resin 100 weight parts.
In addition, in the scope that does not influence the object of the invention, also can cooperate fire retardant, antistatic agent, toughener, properties-correcting agent etc. as required ad lib, its usage quantity also is not particularly limited, and does not get final product so long as do not influence the scope of the object of the invention.
The manufacture method of vinyl chloride resin composition of the present invention is not particularly limited, can use as inferior method manufacturing: the vinyl chloride copolymer resin and the vinyl chloride resin of set amount are cooperated, cooperate the various additive (thermo-stabilizers that use as required, lubricant, stabilizing additive, processing aid, weighting agent, oxidation inhibitor, photostabilizer, pigment, softening agent, and fire retardant, antistatic agent, toughener, properties-correcting agent etc.), use for example ribbon mixer, super mixing machine, tumbler mixer, Banbury mixer, Henschel mixer, mixing machines such as mixing roller and/or mixed milling machine etc. utilize ordinary methods such as hot blend or cold blend to carry out uniform mixing or mixed milling etc.The cooperation sequential scheduling of this moment is not particularly limited, and can use the technology of the scope that does not influence the object of the invention arbitrarily.For example can use: the method for disposable cooperation vinyl chloride resin, vinyl chloride copolymer resin and various additives; In order to cooperate aqueous additive equably, cooperate the various additives of vinyl chloride resin, vinyl chloride copolymer resin and powder body earlier, cooperate the method for aqueous additive then; Or cooperate vinyl chloride resin and vinyl chloride copolymer resin earlier, and cooperate aqueous additive then, cooperate the method for the various additives of powder body at last; Also have to cooperate vinyl chloride resin and various additive earlier, cooperate the method for vinyl chloride copolymer resin etc. then.
The vinyl chloride resin composition of the present invention of Zhi Zaoing can be directly used in various forming process as mentioned above, is used for various forming process after can also using mixing or mixing granulator such as mixing rolls such as common kneader, forcing machine, tablets press and/or mixing granulator machine.
Embodiment
Below, the present invention is described in detail based on embodiment, but the present invention is not limited to following embodiment.Wherein, be not specifically noted " part " expression " weight part " among the embodiment, " % " expression " weight % ".
The manufacturing that has the macromonomer of the polymkeric substance that constitutes by the ethylenically unsaturated monomers that contains two keys on the＜main chain 〉
Have the manufacturing of the macromonomer of the polymkeric substance that constitutes by the ethylenically unsaturated monomers that contains two keys on the main chain, carry out according to the described order of following Production Example.
(Production Example 1)
In the separable flask of the 2L that has return line and stirrer, add CuBr (5.54g), will carry out nitrogen replacement in the reaction vessel.Add acetonitrile (73.8ml), in 70 ℃ of following oil baths, stirred 30 minutes.Add n-butyl acrylate (132g), 2 bromopropionic acid methyl esters (7.2ml), five methyl diethylentriamine (4.69ml) to it, begin reaction.70 ℃ of following heated and stirred, the limit splashed into n-butyl acrylate (528g) continuously with 90 minutes, and reheat stirred 80 minutes.
With the reaction mixture dilution with toluene, after activated alumina column, heat up in a steamer volatile component by decompression, obtain single terminal Br base poly-(n-butyl acrylate).
The methyl alcohol (800ml) of packing in flask is cooled to 0 ℃.To wherein adding tert.-butoxy potassium (130g) several times.This reaction soln is remained on 0 ℃, the methanol solution of the vinylformic acid that drips (100g).Drip finish after, make the temperature of reaction solution get back to room temperature from 0 ℃ after, heat up in a steamer the volatile component of dereaction liquid by decompression, obtain potassium acrylate (CH
2=CHCO
2K).
In having the 500ml flask of return line, add the terminal Br base of the list obtain poly-(n-butyl acrylate) (150g), potassium acrylate (7.45g), N,N-DIMETHYLACETAMIDE (150ml), 70 ℃ of heated and stirred 3 hours.Heat up in a steamer N,N-DIMETHYLACETAMIDE from reaction mixture, in toluene, make its dissolving, after activated alumina column, obtain poly-(n-butyl acrylate) macromonomer of single terminal acryl by heating up in a steamer toluene.
The manufacturing of＜vinyl chloride copolymer resin that the macromonomer copolymerization that has the polymkeric substance that is made of the ethylenically unsaturated monomers that contains two keys on vinyl monomer and the main chain is obtained 〉
The manufacturing of the vinyl chloride copolymer resin that the macromonomer copolymerization that has the polymkeric substance that is made of the ethylenically unsaturated monomers that contains two keys on vinyl monomer and the main chain is obtained is carried out according to the described step of following Production Example.
The branch rate of (Production Example A) macromonomer composition is the manufacturing of 3% vinyl chloride copolymer resin
After having the stainless steel polymerization reactor degassing of 25 liters of inner capacitiess of chuck and stirrer; pack into 97 parts of vinyl chloride monomers; the terminal acryl of list that adds Production Example 1 then gathers 3 parts of (n-butyl acrylate) macromonomers; in chuck, feed warm water then; make that temperature is warming up to 30 ℃ in the polymerization reactor, stirred 5 minutes with the speed of rotation of changeing in per 1 minute 900.In chuck, feed water; the interior temperature of polymerization reactor is cooled to below 20 ℃; then; adding saponification deg is about 80 moles of %, mean polymerisation degree and is about 0.0216 part of 2000 0.1 part of partly-hydrolysed polyvinyl acetate, new peroxide tert-butyl caprate, two (3; 5; 5-trimethyl acetyl base) superoxide is 0.024 part, adds 60 ℃ 150 parts in warm water then, about 6 hours of 66.5 ℃ of polymerizations of polymerization temperature.After unreacted monomer recovery in the polymerizer, the cooling polymerizer makes slurry go out groove.With the slurry dewatering that obtains, 55 ℃ of dryings 24 hours, obtain the white powder of vinylchlorid/poly-(n-butyl acrylate) graft copolymerization Resin A with hot air dryer.
The branch rate of (Production Example B) macromonomer composition is the manufacturing of 5% vinyl chloride copolymer resin
In Production Example A; the terminal acryl of list that adds 95 parts of vinyl chloride monomers and Production Example 1 gathers 5 parts of (n-butyl acrylate) macromonomers; in addition operate equally with Production Example A, obtain the white powder of vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B.
The branch rate of (Production Example C) macromonomer composition is the manufacturing of 20% vinyl chloride copolymer resin
In Production Example A; the terminal acryl of list that adds 80 parts of vinyl chloride monomers and Production Example 1 gathers 20 parts of (n-butyl acrylate) macromonomers; in addition operate equally with Production Example A, obtain the white powder of vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin C.
The branch rate of (Production Example D) macromonomer composition is the manufacturing of 50% vinyl chloride copolymer resin
In Production Example A; the terminal acryl of list that adds 50 parts of vinyl chloride monomers and Production Example 1 gathers 50 parts of (n-butyl acrylate) macromonomers; in addition operate equally with Production Example A, obtain the white powder of vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin D.
(embodiment 1)
With respect to common polyvinyl chloride (PVC) RESINS (the カ ネ PVC ニ one Le S1001: Kanegafuchi Chemical Ind's system that uses, the vinyl chloride homo resin, K value 68) 100 part, with organic tin thermo-stabilizer (TVS#8831: Nitto Kasei Co., Ltd's system, the sulfydryl dioctyl tin) 2 part, diester series lubricant agent (LoxiolG-60: コ グ ニ ス ジ ヤ パ Application Co., Ltd. system) 0.3 part, the partly-hydrolysed ester series lubricant agent of montanic acid (Wax-OP: ヘ キ ス ト ジ ヤ パ Application Co., Ltd. system) 0.3 part, become 110 ℃ with the Henschel mixer mixing until resin temperature, be cooled to then below 50 ℃, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among 2 parts of Production Example B, obtain vinyl chloride resin composition, said composition is made Co., Ltd.'s system HOS-2103 8 inches rollers of type (external diameter is about 20cm) with Japanese ロ one Le, at preliminary roller 20rpm, back roller 18rpm, 180 ℃, under the condition of 5 minutes rollers, make the roller sheet that thickness is about 1mm.The roller sheet that obtains is divided into two parts, and portion tears up the square into about 3mm, is used for the evaluation of melt flow characteristics.In addition, tens of of the size backs that another part is cut into regulation overlap, with the made シ Application of the refreshing rattan metal industry of Co., Ltd. De same form SF type oil pressure press, press down restriction 10 minutes at 185 ℃, pressure 5MPa, make the test plate (panel) of thickness 5mm, then with machining make the softening temperature evaluation with, as each sample of the resistance to impact shock and the tensile strength evaluation usefulness of one of physical strength rerum natura, be used for various mensuration.
Wherein, the evaluation method of melt flow characteristics, softening temperature, resistance to impact shock and tensile strength is as described below.
(1) melt flow characteristics
Flow test method with the thermoplastic resin stipulated in the JIS K7210 appendix C is a benchmark, use highization of the system formula flowing test instrument CFT-500C of Shimadzu Scisakusho Ltd type, under the condition of 180 ℃ of test temperatures, the long 1mm of mould, mould diameter 1mm, trial load 9.8 * 102N, obtain per 1 second resin flow value and (following it is abbreviated as high formula B method yield point value.Unit is ml/s * 10
-2), estimate.
(2) softening temperature
Vicat softening temperature test method with JIS K7206 regulation is a benchmark, 88 hours long 20mm, the test film of wide 20mm, thick 3mm have been left standstill in use in the thermostatic constant wet chamber of 23 ℃ of room temperatures and relative humidity 50%, on-test 40 ℃ of temperature, heat-up rate be under the condition of 50 ℃/h, trial load 50N, obtain vicat softening temperature (below be abbreviated as the Vicat softening temperature.Unit is ℃), estimate.
(3) resistance to impact shock
With the Izod impact strength test method stipulated among the JIS K7110 is benchmark, use has the test film of the breach of type A with machining on the test film of Class1, obtain the Izod shock strength under 23 ℃ and 0 ℃ (below be abbreviated as the Izod shock strength.Unit is kJ/m
2), estimate.Should illustrate, when measuring for 23 ℃, use the test film that in the thermostatic constant wet chamber of 23 ℃ of room temperatures and relative humidity 50%, left standstill 48 hours.In addition, when 0 ℃ was measured, the test film that use will have been left standstill in the thermostatic constant wet chamber of 23 ℃ of room temperatures and relative humidity 50% 48 hours had been adjusted in 0 ℃ the liquid bath again and is flooding the test film that formed in 5 minutes, and after taking out from liquid bath 5 seconds are impacted with interior.
(4) tensile strength
Stretching test method with JIS K7162 regulation is a benchmark, use has been left standstill 48 hours test film with 1A type test film in the thermostatic constant wet chamber of 23 ℃ of room temperatures and relative humidity 50%, obtain tensile strength under trial speed 10mm/min, 23 ℃ (below be designated as σ y.Unit is MPa), estimate.
The result is as shown in table 1.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.1 part.
(embodiment 2)
In embodiment 1, substitute vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among the Production Example B, but per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization Resin A that obtains among 10 parts of Production Example A, in addition operation similarly to Example 1, obtain vinyl chloride resin composition, said composition is carried out roller/pressure processing similarly to Example 1, estimate high formula B method yield point value, Vicat softening temperature, Izod shock strength and σ y.The result is as shown in table 1.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.3 part.
(embodiment 3)
In embodiment 1, substitute vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among the Production Example B, but per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin C that obtains among 0.5 part of Production Example C, in addition operation similarly to Example 1, obtain vinyl chloride resin composition, said composition is carried out roller/pressure processing similarly to Example 1, estimate high formula B method yield point value, Vicat softening temperature, Izod shock strength and σ y.The result is as shown in table 1.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.1 part.
(embodiment 4)
In embodiment 3, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate 5 parts of vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin C, in addition operation similarly to Example 3, obtain vinyl chloride resin composition, said composition is carried out roller/pressure processing similarly to Example 3, estimate high formula B method yield point value, Vicat softening temperature, Izod shock strength and σ y.The result is as shown in table 1.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 1 part.
(embodiment 5)
In embodiment 1, substitute vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among the Production Example B, but per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin D that obtains among 0.2 part of Production Example D, in addition operation similarly to Example 1, obtain vinyl chloride resin composition, said composition is carried out roller/pressure processing similarly to Example 1, estimate high formula B method yield point value, Vicat softening temperature, Izod shock strength and σ y.The result is as shown in table 1.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.1 part.
(embodiment 6)
In embodiment 5, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate 10 parts of vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin D, in addition operation similarly to Example 5, obtain vinyl chloride resin composition, said composition is carried out roller/pressure processing similarly to Example 5, estimate high formula B method yield point value, Vicat softening temperature, Izod shock strength and σ y.The result is as shown in table 1.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 5 parts.
(comparative example 1)
In embodiment 1, mismatch vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among the Production Example B, in addition operation similarly to Example 1, obtain vinyl chloride resin composition, said composition is carried out roller/pressure processing similarly to Example 1, estimate high formula B method yield point value, Vicat softening temperature, Izod shock strength and σ y.The result is as shown in table 1.High formula B method yield point value, Izod shock strength and σ y are all low than embodiment 1～6, not preferred.
(comparative example 2)
In comparative example 1, further cooperate 10 parts of di-2-ethylhexyl phthalates as softening agent (goods name DOP, the ジ エ イ プ ラ ス of Co., Ltd. system, below be abbreviated as DOP), in addition operate equally with comparative example 1, obtain vinyl chloride resin composition, said composition and comparative example 1 are carried out roller/pressure processing equally, estimate high formula B method yield point value, Vicat softening temperature, Izod shock strength and σ y.The result is as shown in table 1.Vicat softening temperature, Izod shock strength and σ y are all low than comparative example 1, and be not preferred.
(comparative example 3)
In comparative example 1, further cooperate methyl methacrylate class processing aid (メ Block レ Application P-551A: Mitsubishi Rayon Co. Ltd.'s system) 2 parts, in addition operate equally with comparative example 1, obtain vinyl chloride resin composition, said composition and comparative example 1 are carried out roller/pressure processing equally, estimate high formula B method yield point value, Vicat softening temperature, Izod shock strength and σ y.The result is as shown in table 1.Vicat softening temperature, Izod shock strength and σ y are all low than comparative example 1, and be not preferred.
(comparative example 4)
In comparative example 1, further cooperate and impact toughener (メ Block レ Application C-323A: Mitsubishi Rayon Co. Ltd.'s system, the MBS resin) 3 part, in addition operate equally with comparative example 1, obtain vinyl chloride resin composition, said composition and comparative example 1 are carried out roller/pressure processing equally, estimate high formula B method yield point value, Vicat softening temperature, Izod shock strength and σ y.The result is as shown in table 1.High formula B method yield point value, Vicat softening temperature and σ y are comparative example below 1, and it is insufficient to improve effect.
(comparative example 5)
In embodiment 2, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization Resin A that obtains among 1 part of Production Example A, in addition operation similarly to Example 1, obtain vinyl chloride resin composition, said composition is carried out roller/pressure processing similarly to Example 1, estimate high formula B method yield point value, Vicat softening temperature, Izod shock strength and σ y.The result is as shown in table 1.The characteristic value of estimating is comparative example below 1, and it is insufficient to improve effect.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.03 part.
(comparative example 6)
In comparative example 5, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin D that obtains among 20 parts of Production Example D, in addition operation similarly to Example 5, obtain vinyl chloride resin composition, said composition is carried out roller/pressure processing similarly to Example 5, estimate high formula B method yield point value, Vicat softening temperature, Izod shock strength and σ y.The result is as shown in table 1.Vicat softening temperature, Izod shock strength and σ y are all low than comparative example 1, and be not preferred.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 10 parts.
Table 1
| The macromonomer composition accounts for the branch rate (weight %) of whole vinyl chloride copolymer resins: X | The interpolation umber (weight part) of per 100 weight part vinyl chloride resin vinyl chloride copolymer resins: Y | With vinyl chloride resin 100 weight parts is the content (weight part) of the macromonomer composition of benchmark: Z *1) | The kind and the umber of the additive beyond vinyl chloride resin, vinyl chloride copolymer resin, thermo-stabilizer, the lubricant | High formula B method yield point value ml/s * 10 -2 | The Vicat softening temperature (℃) | Izod shock strength (kJ/m 2) | σy (MPa) | |||
| 0℃ | 23℃ | |||||||||
| Embodiment | 1 | 5 | 2 | 0.1 | Do not have | 2.5 | 80.2 | 3.3 | 6.3 | 48.2 |
| 2 | 3 | 10 | 0.3 | Do not have | 3.3 | 80.0 | 3.5 | 6.8 | 49.3 | |
| 3 | 20 | 0.5 | 0.1 | Do not have | 2.8 | 80.2 | 3.2 | 6.0 | 47.8 | |
| 4 | 20 | 5 | 1 | Do not have | 4.0 | 79.8 | 3.8 | 7.3 | 49.7 | |
| 5 | 50 | 0.2 | 0.1 | Do not have | 3.0 | 80.2 | 3.2 | 6.0 | 48.0 | |
| 6 | 50 | 10 | 5 | Do not have | 5.4 | 79.2 | 4.0 | 7.5 | 50.1 | |
| Comparative example | 1 | - | 0 | 0 | Do not have | 0.6 | 80.0 | 3.0 | 4.7 | 46.0 |
| 2 | - | 0 | 0 | D0P 10 weight parts | 7.6 | 66.2 | 3.5 | 5.0 | 38.9 | |
| 3 | - | 0 | 0 | Processing aid *2)2 weight parts | 1.0 | 80.2 | 2.5 | 3.8 | 41.8 | |
| 4 | - | 0 | 0 | MBS resin 3 weight parts | 0.7 | 80.5 | 7.5 | 9.8 | 43.5 | |
| 5 | 3 | 1 | 0.03 | Do not have | 0.6 | 78.0 | 2.9 | 4.6 | 45.9 | |
| 6 | 50 | 20 | 10 | Do not have | 10.2 | 73.6 | 3.0 | 3.7 | 42.3 | |
* 1) with vinylchlorid/when poly-(n-butyl acrylate) graft copolymerization resin is added on and uses in the polyvinyl chloride (PVC) RESINS, the value of calculating by following formula.
Z＝X×Y÷100
Z: with vinyl chloride resin 100 weight parts is the content (weight part) of the macromonomer composition of benchmark
X: the macromonomer composition accounts for the branch rate (weight %) of whole vinyl chloride copolymer resins
Y: with respect to vinyl chloride resin 100 weight parts, the interpolation umber (weight part) of vinyl chloride copolymer resin
* 2) processing aid: methyl methacrylate class processing aid
(embodiment 7)
With respect to common polyvinyl chloride (PVC) RESINS (the カ ネ PVC ニ one Le S1008: Kanegafuchi Chemical Ind's system that uses, the vinyl chloride homo resin, K value 60) 100 part, with organic tin thermo-stabilizer (T-17MOK: Common medicine Co., Ltd's system, the sulfydryl tin octylate) 1.2 part, polymer complex ester series lubricant agent (Loxiol G-74: コ グ ニ ス ジ ヤ パ Application Co., Ltd. system) 1.6 parts, polyol ester series lubricant agent (Loxiol G-16: コ グ ニ ス ジ ヤ パ Application Co., Ltd. system) 0.9 part, impact toughener (カ ネ エ one ス B-51: Kanegafuchi Chemical Ind's system, MBS, below be abbreviated as the MBS resin) 10 parts, become 110 ℃ with the Henschel mixer mixing until resin temperature, be cooled to then below 50 ℃, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among 2 parts of Production Example B, obtain vinyl chloride resin composition, said composition is made Co., Ltd.'s system H0S-2103 8 inches rollers of type (external diameter is about 20cm) with Japanese ロ one Le, at preliminary roller 15rpm, back roller 16rpm, 180 ℃, under the condition of 3 minutes rollers, make thick about 1.0mm, the roller sheet of wide 30cm.This roller sheet of visual observations, according to following benchmark with 5 grade evaluation air marks.
5: can't see air marks fully
4: almost can't see air marks
3: can see air marks, but practical no problem
2: produce air marks, in practicality, have problems
1: the generation of air marks is obvious, and sheet surface is poor
The result is as shown in table 2.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.1 part.
In addition, with respect to common polyvinyl chloride (PVC) RESINS (the カ ネ PVC ニ one Le S1008: Kanegafuchi Chemical Ind's system that uses, the vinyl chloride homo resin, K value 60) 100 part, with organic tin thermo-stabilizer (MARK 17M: Network ロ Application プ ト Application Co., Ltd. system, the sulfydryl tin octylate) 1 part, special esters series lubricant agent (Loxiol G-70S: コ グ ニ ス ジ ヤ パ Application Co., Ltd. system) 0.3 part, polyol ester series lubricant agent (Loxiol G-16: コ グ ニ ス ジ ヤ パ Application Co., Ltd. system) 0.4 part, impact toughener (カ ネ エ one ス B-521: Kanegafuchi Chemical Ind's system, the MBS resin) 6 part, become 110 ℃ with the Henschel mixer mixing until resin temperature, be cooled to then below 50 ℃, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among 2 parts of Production Example B, obtain vinyl chloride resin composition, said composition is made Co., Ltd.'s system H0S-2103 8 inches rollers of type (external diameter is about 20cm) with Japanese ロ one Le, at preliminary roller 17rpm, back roller 16rpm, 200 ℃, under the condition of 3 minutes rollers, make thick about 0.5mm, the roller sheet of wide 35cm.This roller sheet of visual observations, according to following benchmark with 5 grade evaluation ripples.
5: can't see ripple fully
4: almost can't see ripple
3: can see ripple, but practical no problem
2: produce ripple, existing problems in the practicality
1: the generation of ripple is obvious, and sheet surface is poor
The result is as shown in table 2.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.1 part.
(embodiment 8)
In embodiment 7, substitute vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among the Production Example B, but per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin C that obtains among 0.5 part of Production Example C, in addition operation similarly to Example 7, obtain vinyl chloride resin composition, said composition is carried out roll-in similarly to Example 7, estimate air marks and ripple.The result is as shown in table 2.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.1 part.
(embodiment 9)
In embodiment 8, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate 5 parts of vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin C, and in addition operation similarly to Example 8 obtains vinyl chloride resin composition, said composition is carried out roll-in similarly to Example 8, estimate air marks and ripple.The result is as shown in table 2.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 1 part.
(embodiment 10)
In embodiment 7, substitute vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among the Production Example B, but per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin D that obtains among 0.2 part of Production Example D, in addition operation similarly to Example 7, obtain vinyl chloride resin composition, said composition is carried out roll-in similarly to Example 7, estimate air marks and ripple.The result is as shown in table 2.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.1 part.
(embodiment 11)
In embodiment 10, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate 10 parts of vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin D, and in addition operation similarly to Example 10 obtains vinyl chloride resin composition, said composition is carried out roll-in similarly to Example 10, estimate air marks and ripple.The result is as shown in table 2.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 5 parts.
(comparative example 7)
In embodiment 7, mismatch vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among the Production Example B, in addition operation similarly to Example 7 obtains vinyl chloride resin composition, said composition is carried out roll-in similarly to Example 1, estimate air marks and ripple.The result is as shown in table 2.Air marks and ripple are all poor than embodiment 7～11, and be not preferred.
(comparative example 8)
In comparative example 7, further cooperate methyl methacrylate class processing aid (メ Block レ Application P-551A: Mitsubishi Rayon Co. Ltd.'s system) 2 parts, in addition operate equally with comparative example 7, obtain vinyl chloride resin composition, said composition and comparative example 7 are carried out roll-in equally, estimate air marks and ripple.The result is as shown in table 2.Ripple is poorer than embodiment 7～11, and it is insufficient to improve effect.
(comparative example 9)
In comparative example 7, further cooperate 10 parts of di-2-ethylhexyl phthalates as softening agent (goods name DOP, the ジ エ イ プ ラ ス of Co., Ltd. system, below be abbreviated as DOP), in addition operate equally with comparative example 7, obtain vinyl chloride resin composition, said composition and comparative example 7 are carried out roll-in equally, estimate air marks and ripple.The result is as shown in table 2.Ripple is poorer than embodiment 7～11, and it is insufficient to improve effect.
(comparative example 10)
In embodiment 7, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among 1 part of Production Example B, in addition operation similarly to Example 7, obtain vinyl chloride resin composition, said composition is carried out roll-in similarly to Example 7, estimate air marks and ripple.The result is as shown in table 2.Air marks is poorer than embodiment 7～11, and it is insufficient to improve effect.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.05 part.
(comparative example 11)
In embodiment 8, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin C that obtains among 0.1 part of Production Example C, in addition operation similarly to Example 8, obtain vinyl chloride resin composition, said composition is carried out roll-in similarly to Example 2, estimate air marks and ripple.The result is as shown in table 2.Air marks and ripple are all poor than embodiment 7～11, and be not preferred.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.02 part.
(comparative example 12)
In embodiment 8, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin C that obtains among 30 parts of Production Example C, in addition operation similarly to Example 8, obtain vinyl chloride resin composition, said composition is carried out roll-in similarly to Example 8, estimate air marks and ripple.The result is as shown in table 2.Air marks and ripple are all poor than embodiment 7～11, and be not preferred.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 6 parts.
(comparative example 13)
In embodiment 10, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin D that obtains among 0.1 part of Production Example D, in addition operation similarly to Example 10, obtain vinyl chloride resin composition, said composition is carried out roll-in similarly to Example 10, estimate air marks and ripple.The result is as shown in table 2.Ripple is poorer than embodiment 7～11, and it is insufficient to improve effect.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.05 part.
(comparative example 14)
In embodiment 10, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin D that obtains among 20 parts of Production Example D, in addition operation similarly to Example 10, obtain vinyl chloride resin composition, said composition is carried out roll-in similarly to Example 10, estimate air marks and ripple.The result is as shown in table 2.Air marks and ripple are all poor than embodiment 7～11, and be not preferred.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 10 parts.
Table 2
| The macromonomer composition accounts for the branch rate (weight %) of whole vinyl chloride copolymer resins: X | The use umber (weight part) of vinyl chloride copolymer resin: Y | With vinyl chloride resin 100 weight parts is the content (weight part) of the macromonomer composition of benchmark: Z *1) | Processing aid adds umber (weight part) *2) | Softening agent adds umber (weight part) *3) | Air marks *4) | Ripple *4) | ||
| Embodiment | 7 | 5 | 2 | 0.1 | 0 | 0 | 5 | 4 |
| 8 | 20 | 0.5 | 0.1 | 0 | 0 | 5 | 5 | |
| 9 | 20 | 5 | 1 | 0 | 0 | 4 | 5 | |
| 10 | 50 | 0.2 | 0.1 | 0 | 0 | 5 | 5 | |
| 11 | 50 | 10 | 5 | 0 | 0 | 3 | 3 | |
| Comparative example | 7 | - | 0 | 0 | 0 | 0 | 1 | 1 |
| 8 | - | 0 | 0 | 2 | 0 | 4 | 2 | |
| 9 | - | 0 | 0 | 0 | 10 | 3 | 2 | |
| 10 | 5 | 1 | 0.05 | 0 | 0 | 2 | 3 | |
| 11 | 20 | 0.1 | 0.02 | 0 | 0 | 2 | 2 | |
| 12 | 20 | 30 | 6 | 0 | 0 | 2 | 1 | |
| 13 | 50 | 0.1 | 0.05 | 0 | 0 | 3 | 2 | |
| 14 | 50 | 20 | 10 | 0 | 0 | 2 | 1 | |
* 1) with vinylchlorid/when poly-(n-butyl acrylate) graft copolymerization resin is added on and uses in the polyvinyl chloride (PVC) RESINS, the value of calculating by following formula.
Z=X * Y ÷ 100 is Z wherein: the content (weight part) that with vinyl chloride resin 100 weight parts is the macromonomer composition of benchmark
X: the macromonomer composition accounts for the branch rate (weight %) of whole vinyl chloride copolymer resins
Y: with respect to vinyl chloride resin 100 weight parts, the interpolation umber (weight part) of vinyl chloride copolymer resin
* 2) processing aid: methyl methacrylate class processing aid
* 3) softening agent: DOP
* 4) the determinating reference of air marks and ripple
Air marks 5: can't see air marks ripple 5 fully: can't see ripple fully
4: almost can't see air marks 4: almost can't see ripple
3: can see air marks, but practicality goes up no problem 3: can see ripple, but practical no problem
2: produce air marks, have the practical problem 2 that goes up: produce ripple, have the practical problem that goes up
1: the generation of air marks is obvious, and sheet surface differs from 1: the generation of ripple is obvious, and sheet surface is poor
(embodiment 12)
With respect to common polyvinyl chloride (PVC) RESINS (the カ ネ PVC ニ one Le S1007: Kanegafuchi Chemical Ind's system that uses, the vinyl chloride homo resin, K value 57) 100 part, with organic tin thermo-stabilizer (TVS#8831: Nitto Kasei Co., Ltd's system, the sulfydryl dioctyl tin) 2.0 part, oxidic polyethylene series lubricant agent (ACPE629A: ア ラ イ De ケ ミ カ Le Co., Ltd. system) 0.2 part, diester series lubricant agent (Loxiol G-60: コ グ ニ ス ジ ヤ パ Application Co., Ltd. system) 0.5 part, become 110 ℃ with the Henschel mixer mixing until resin temperature, be cooled to then below 50 ℃, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among 2 parts of Production Example B, obtain vinyl chloride resin composition.Said composition is supplied with single screw extrusion machine (the system VS50m/m of limit, field plastics Co., Ltd. forcing machine FH50-239), will spray tow and carry out granulation with tablets press (the system plastics processor SCF-100 of い The ず chemical industry machine Co., Ltd.).With this pellet supply injection moulding machine (the system AUTOSHOT T Series 75D of FANUC society), estimate helical flow.The result is as shown in table 3.Helical flow length grows up to the good fluidity that type adds man-hour more.
Then, use with injection moulding machine moulding resistance to impact shock (Izod shock strength) and estimate, supply with and estimate with rectangle and tensile strength (σ y) evaluation dumbbell specimen.The result is as shown in table 3.
The as described below setting of various conditions of granulation, helical flow evaluation, rectangle and dumbbell specimen moulding should be described.
＜granulation condition 〉
Screw rod revolution: 30rpm
Barrel temperature
Barrel-1:150 ℃
Barrel-2:170 ℃
Barrel-3:180 ℃
Annotate: the barrel sequence number be from raw material supplying side (loading hopper side) to extrude direction, promptly to screw front end, number by 1,2,3 order.
The head mould temperature
Mould 1:190 ℃
Mould 2:190 ℃
Annotate: the mould sequence number be from screw front end to extruding direction, number by 1,2 order.
＜helical flow evaluation 〉
The injecting unit temperature
Unit 1:170 ℃
Unit 2:180 ℃
Unit 3:190 ℃
Annotate: unit number be from raw material supplying side (loading hopper side) to extrude direction, promptly to screw front end, number by 1,2,3 order.
Nozzle temperature: 190 ℃
Die temperature: 40 ℃
Injection speed: 50mm/s
Pressurize: 1300kg/cm
2
The pressurize hold-time: 3sec
Injection pressurize switching position: 2mm
Maximum injection pressure: 1300kg/cm
2
The maximum injection time: 3sec
Maximum pressurize speed: 5mm/s
Back pressure: 100kg/cm
2
Screw rod revolution: 50rpm
Cooling time: 20sec
＜rectangle and dumbbell specimen moulding 〉
The injecting unit temperature
Unit 1:170 ℃
Unit 2:180 ℃
Unit 3:190 ℃
Annotate: unit number be from raw material supplying side (loading hopper side) to extrude direction, promptly to screw front end, number by 1,2,3 order.
Nozzle temperature: 190 ℃
Die temperature: 40 ℃
Injection speed: 20mm/s
Pressurize: 800kg/cm
2
The pressurize hold-time: 5sec
Injection pressurize switching position: 5mm
Maximum injection pressure: 1500kg/cm
2
The maximum injection time: 5sec
Maximum pressurize speed: 5mm/s
Back pressure: 100kg/cm
2
Screw rod revolution: 50rpm
Cooling time: 20sec
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.1 part.
(embodiment 13)
In embodiment 12, substitute vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among the Production Example B, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin C that obtains among 0.5 part of Production Example C, in addition operation similarly to Example 12, obtain vinyl chloride resin composition, with said composition usefulness method similarly to Example 12, estimate helical flow length, Izod shock strength and σ y.The result is as shown in table 3.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.1 part.
(embodiment 14)
In embodiment 13, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate 5 parts of vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin C, in addition operation similarly to Example 13, obtain vinyl chloride resin composition, with said composition usefulness method similarly to Example 13, estimate helical flow length, Izod shock strength and σ y.The result is as shown in table 3.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 1 part.
(embodiment 15)
In embodiment 12, substitute vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among the Production Example B, but per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin D that obtains among 0.2 part of Production Example D, in addition operation similarly to Example 12, obtain vinyl chloride resin composition, with said composition usefulness method similarly to Example 12, estimate helical flow length, Izod shock strength and σ y.The result is as shown in table 3.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.1 part.
(embodiment 16)
In embodiment 15, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate 2 parts of vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin D, in addition operation similarly to Example 15, obtain vinyl chloride resin composition, with said composition usefulness method similarly to Example 15, estimate helical flow length, Izod shock strength and σ y.The result is as shown in table 3.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 1 part.
(comparative example 15)
In embodiment 12, mismatch vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among the Production Example B, in addition operation similarly to Example 12, obtain vinyl chloride resin composition, with said composition usefulness method similarly to Example 12, estimate helical flow length, Izod shock strength and σ y.The result is as shown in table 3.The value of helical flow length, Izod shock strength and σ y is all low than embodiment 12～16, and is not preferred.
(comparative example 16)
In comparative example 15, further cooperate and impact toughener (メ Block レ Application C-323A: Mitsubishi Rayon Co. Ltd.'s system, the MBS resin) 3 part, in addition operate equally with comparative example 15, obtain vinyl chloride resin composition, with the said composition method same, estimate helical flow length, Izod shock strength and σ y with comparative example 15.The result is as shown in table 3.The value of helical flow length and σ y is all low than embodiment 12～16, and it is insufficient to improve effect.
(comparative example 17)
In comparative example 16, substitute the impact toughener and cooperate CPE (the ダ イ ソ of Co., Ltd. one system, ダ イ ソ ラ Star Network H-135) 3 part, in addition operate equally with comparative example 16, obtain vinyl chloride resin composition, with the said composition method same, estimate helical flow length, Izod shock strength and σ y with comparative example 16.The result is as shown in table 3.The value of helical flow length and σ y is all low than embodiment 12～16, and it is insufficient to improve effect.
(comparative example 18)
In comparative example 16, substitute to impact toughener and cooperate di-2-ethylhexyl phthalate (goods name DOP as softening agent, the ジ エ イ プ ラ ス of Co., Ltd. system, be designated hereinafter simply as DOP) 5 parts, in addition operate equally with comparative example 16, obtain vinyl chloride resin composition,, estimate helical flow length, Izod shock strength and σ y the said composition method same with comparative example 16.The result is as shown in table 1.The value of Izod shock strength and σ y is all low than embodiment 12～16, and it is insufficient to improve effect.
(comparative example 19)
In comparative example 16, substitute the impact toughener and cooperate methyl methacrylate class processing aid (メ Block レ Application P-551A: Mitsubishi Rayon Co. Ltd.'s system) 1 part, in addition operate equally with comparative example 16, obtain vinyl chloride resin composition, with the said composition method same, estimate helical flow length, Izod shock strength and σ y with comparative example 16.The result is as shown in table 3.The value of helical flow length and σ y is all low than embodiment 12～16, and it is insufficient to improve effect.
(comparative example 20)
In embodiment 12, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among 1 part of Production Example B, in addition operation similarly to Example 12, obtain vinyl chloride resin composition, with said composition usefulness method similarly to Example 12, estimate helical flow length, Izod shock strength and σ y.The result is as shown in table 3.The value of helical flow length, Izod shock strength and σ y is all low and comparative example 15 is roughly equal than embodiment 12～16, and it is insufficient to improve effect.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.05 part.
(comparative example 21)
In embodiment 15, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin D that obtains among 3 parts of Production Example D, in addition operation similarly to Example 15, obtain vinyl chloride resin composition, with said composition usefulness method similarly to Example 15, estimate helical flow length, Izod shock strength and σ y.The result is as shown in table 3.The value of Izod shock strength and σ y is all low than embodiment 12～16, and it is insufficient to improve effect.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 1.5 parts.
Table 3
| The macromonomer composition accounts for the branch rate (weight %) of whole vinyl chloride copolymer resins: X | Interpolation umber (weight part) with respect to the vinyl chloride copolymer resin of 100 weight part vinyl chloride resins: Y | With vinyl chloride resin 100 weight parts is the content (weight part) of the macromonomer composition of benchmark: Z *1) | The kind and the umber of the additive beyond vinyl chloride resin, vinyl chloride copolymer resin, thermo-stabilizer, the lubricant | Helical flow length (mm) | Izod shock strength (kJ/m 2) | σy (MPa) | ||
| Embodiment | 12 | 5 | 2 | 0.1 | Do not have | 435 | 3.3 | 50.7 |
| 13 | 20 | 0.5 | 0.1 | Do not have | 430 | 3.2 | 50.8 | |
| 14 | 20 | 5 | 1 | Do not have | 460 | 3.4 | 51.3 | |
| 15 | 50 | 0.2 | 0.1 | Do not have | 425 | 3.3 | 51.0 | |
| 16 | 50 | 2 | 1 | Do not have | 455 | 3.5 | 50.9 | |
| Comparative example | 15 | - | 0 | 0 | Do not have | 400 | 3.1 | 50.6 |
| 16 | - | 0 | 0 | MBS resin 3 weight parts | 385 | 5.0 | 47.8 | |
| 17 | - | 0 | 0 | CPE 3 weight parts | 415 | 3.1 | 48.1 | |
| 18 | - | 0 | 0 | DOP 5 weight parts | 425 | 2.7 | 40.0 | |
| 19 | - | 0 | 0 | Processing aid *2)1 weight part | 415 | 3.3 | 46.0 | |
| 20 | 5 | 1 | 0.05 | Do not have | 400 | 3.2 | 50.0 | |
| 21 | 50 | 3 | 1.5 | Do not have | 470 | 2.5 | 45.2 | |
* 1) with vinylchlorid/when poly-(n-butyl acrylate) graft copolymerization resin is added on and uses in the polyvinyl chloride (PVC) RESINS, the value of calculating by following formula.
Z=X * Y ÷ 100 is Z wherein: the content (weight part) that with vinyl chloride resin 100 weight parts is the macromonomer composition of benchmark
X: the macromonomer composition accounts for the branch rate (weight %) of whole vinyl chloride copolymer resins
Y: with respect to vinyl chloride resin 100 weight parts, the interpolation umber (weight part) of vinyl chloride copolymer resin
* 2) processing aid: methyl methacrylate class processing aid
(embodiment 17)
With respect to common polyvinyl chloride (PVC) RESINS (the カ ネ PVC ニ one Le S1001: Kanegafuchi Chemical Ind's system that uses, the vinyl chloride homo resin, K value 68) 100 part, with organic tin thermo-stabilizer (TM694: win field Chemical Co., Ltd system, mercapto methyl tin) 1.0 parts, 0.5 part of special fatty acid ester series lubricant agent (リ ケ ス one SL-02: reason is ground PVC ミ Application Co., Ltd. system), polyethylene kind lubricant (Ha イ ワ Star Network ス 220MP: Mitsui Chemicals, Inc's system) 0.3 part, paraffin class lubricant (H-155: this Jing of Ri Pewter Co., Ltd. system) 0.2 part, weighting agent (calcene CCR: Shiraishi Kogyo Kaisha Ltd.'s system, lime carbonate) 3.0 parts, become 110 ℃ with the Henschel mixer mixing until resin temperature, be cooled to then below 50 ℃, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among 2 parts of Production Example B, obtain vinyl chloride resin composition.Said composition is supplied with コ ニ カ Le forcing machine, and (Toshiba Corporation's system TEC/55DV), is shaped to Φ 75 pipes (internal diameter 75mm, wall thickness 5mm).Cut out test film by the pipe that obtains, estimate resistance to impact shock (Izod shock strength) and fracture toughness property intensity (slope value).The result is as shown in table 4.
Should illustrate that the measuring method of fracture toughness property intensity is as described below.Promptly, according to " the Fracture Characterization of Tough Polymers Using theJ Method " of " Polymer Eng.and Sci. " 26,760 (1986) record of S.Hashemi and J.G.Williams, obtain apparent Jc and the slope value is estimated.
That is, obtain the length Δ a of crackle, at this moment will impose on the energy (kJ/m of crackle by thickness of sample and crackle area
2) map with Δ a, obtain straight line.The value of this straight line when Δ a=0 is called apparent Jc value, represents that new crackle generates the required energy of beginning.In addition, this collinear slope (slope value) expression advances the required energy of crackle, all is the value of reflection fracture toughness property.In the present embodiment, estimate fracture toughness property intensity with the slope value especially.It is big more that the slope value becomes, and advance the required energy of crackle big more, thereby the slope value is big more, and fracture toughness property intensity is high more.
As described below setting of various conditions during the pipe moulding should be described.
Screw rod revolution: 15rpm
Feeder revolution: 10rpm
Barrel temperature
Barrel-1:180 ℃
Barrel-2:180 ℃
Barrel-3:175 ℃
Barrel-4:175 ℃
Annotate: the barrel sequence number be from raw material supplying side (loading hopper side) to extrude direction, promptly to screw front end, number by 1,2,3,4 order.
The head mould temperature
Mould 1:170 ℃
Mould 2:180 ℃
Mould 3:185 ℃
Mould 4:195 ℃
Mould 5:200 ℃
Annotate: the mould sequence number be from screw front end to extruding direction, number by 1,2,3,4,5 order.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.1 part.
(embodiment 18)
In embodiment 17, substitute vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among the Production Example B, but per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin C that obtains among 0.5 part of Production Example C, in addition operation similarly to Example 17, obtain vinyl chloride resin composition, said composition is carried out moulding and cutting similarly to Example 17, estimate Izod shock strength and slope value.The result is as shown in table 4.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.1 part.
(embodiment 19)
In embodiment 18, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate 5 parts of vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin C, in addition operation similarly to Example 18, obtain vinyl chloride resin composition, said composition is carried out moulding and cutting similarly to Example 18, estimate Izod shock strength and slope value.The result is as shown in table 4.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 1 part.
(embodiment 20)
In embodiment 17, substitute vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among the Production Example B, but per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin D that obtains among 0.2 part of Production Example D, in addition operation similarly to Example 17, obtain vinyl chloride resin composition, said composition is carried out moulding and cutting similarly to Example 17, estimate Izod shock strength and slope value.The result is as shown in table 4.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.1 part.
(embodiment 21)
In embodiment 20, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate 10 parts of vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin D, in addition operation similarly to Example 20, obtain vinyl chloride resin composition, said composition is carried out moulding and cutting similarly to Example 20, estimate Izod shock strength and slope value.The result is as shown in table 4.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 5 parts.
(comparative example 22)
In embodiment 17, mismatch vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among the Production Example B, in addition operation similarly to Example 17, obtain vinyl chloride resin composition, said composition is carried out moulding and cutting similarly to Example 17, estimate Izod shock strength and slope value.The result is as shown in table 4.Izod shock strength and slope value are all low than embodiment 17～21, and be not preferred.
(comparative example 23)
In comparative example 22, further cooperate and impact toughener (メ Block レ Application C-323A: Mitsubishi Rayon Co. Ltd.'s system, the MBS resin) 3 part, in addition operate equally with comparative example 22, obtain vinyl chloride resin composition, said composition and comparative example 22 are carried out moulding and cutting equally, estimate Izod shock strength and slope value.The result is as shown in table 4.The slope value is lower than embodiment 17～21, and it is insufficient to improve effect.
(comparative example 24)
In comparative example 23, cooperate and impact 6 parts of tougheners, in addition operate equally with comparative example 23, obtain vinyl chloride resin composition, said composition and comparative example 23 are carried out moulding and cutting equally, estimate Izod shock strength and slope value.The result is as shown in table 4.The slope value is lower than embodiment 17～21, and it is insufficient to improve effect.
(comparative example 25)
In embodiment 17, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin B that obtains among 1 part of Production Example B, in addition operation similarly to Example 17, obtain vinyl chloride resin composition, said composition is carried out moulding and cutting similarly to Example 17, estimate Izod shock strength and slope value.The result is as shown in table 4.Izod shock strength and slope value are all low than embodiment 17～21, and it is insufficient to improve effect.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.05 part.
(comparative example 26)
In embodiment 18, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin C that obtains among 0.1 part of Production Example C, in addition operation similarly to Example 18, obtain vinyl chloride resin composition, said composition is carried out moulding and cutting similarly to Example 18, estimate Izod shock strength and slope value.The result is as shown in table 4.Izod shock strength and slope value are all low than embodiment 17～21, and it is insufficient to improve effect.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.02 part.
(comparative example 27)
In embodiment 18, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin C that obtains among 30 parts of Production Example C, in addition operation similarly to Example 18, obtain vinyl chloride resin composition, said composition is carried out moulding and cutting similarly to Example 18, estimate Izod shock strength and slope value.The result is as shown in table 4.Izod shock strength and slope value are all low than embodiment 17～21, and it is insufficient to improve effect.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 6 parts.
(comparative example 28)
In embodiment 20, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin D that obtains among 0.1 part of Production Example D, in addition operation similarly to Example 20, obtain vinyl chloride resin composition, said composition is carried out moulding and cutting similarly to Example 20, estimate Izod shock strength and slope value.The result is as shown in table 4.Izod shock strength and slope value are all low than embodiment 17～21, and it is insufficient to improve effect.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 0.05 part.
(comparative example 29)
In embodiment 20, per 100 parts of polyvinyl chloride (PVC) RESINS cooperate vinylchlorid/poly-(n-butyl acrylate) graft copolymerization resin D that obtains among 20 parts of Production Example D, in addition operation similarly to Example 20, obtain vinyl chloride resin composition, said composition is carried out moulding and cutting similarly to Example 20, estimate Izod shock strength and slope value.The result is as shown in table 4.Izod shock strength and slope value are all low than embodiment 17～21, and it is insufficient to improve effect.
Should illustrate that said composition is a benchmark with 100 parts of polyvinyl chloride (PVC) RESINS, the content of poly-(n-butyl acrylate) macromonomer composition is 10 parts.
Table 4
| The macromonomer composition accounts for the branch rate (weight %) of whole vinyl chloride copolymer resins: X | Interpolation umber (weight part) with respect to the vinyl chloride copolymer resin of 100 weight part vinyl chloride resins: Y | With vinyl chloride resin 100 weight parts is the content (weight part) of the macromonomer composition of benchmark: Z *1) | Impact the interpolation umber (weight part) of toughener *2) | Izod shock strength (kJ/m 2) | The slope value | |||
| 0℃ | 23℃ | |||||||
| Embodiment | 17 | 5 | 2 | 0.1 | 0 | 6.8 | 10.8 | 28.8 |
| 18 | 20 | 0.5 | 0.1 | 0 | 6.5 | 10.3 | 26.7 | |
| 19 | 20 | 5 | 1 | 0 | 7.3 | 11.1 | 30.5 | |
| 20 | 50 | 0.2 | 0..1 | 0 | 6.0 | 9.7 | 25.0 | |
| 21 | 50 | 10 | 5 | 0 | 5.9 | 9.2 | 33.8 | |
| Comparative example | 22 | - | 0 | 0 | 0 | 3.0 | 3.7 | 18.8 |
| 23 | - | 0 | 0 | 3 | 7.5 | 9.2 | 20.3 | |
| 24 | - | 0 | 0 | 6 | 10.5 | 13.7 | 21.9 | |
| 25 | 5 | 1 | 0.05 | 0 | 3.3 | 4.0 | 19.8 | |
| 26 | 20 | 0.1 | 0.02 | 0 | 3.0 | 3.8 | 19.0 | |
| 27 | 20 | 30 | 6 | 0 | 3.7 | 6.6 | 21.8 | |
| 28 | 50 | 0.1 | 0.05 | 0 | 3.1 | 3.5 | 19.3 | |
| 29 | 50 | 20 | 10 | 0 | 4.0 | 7.5 | 22.2 | |
* 1) with vinylchlorid/when poly-(n-butyl acrylate) graft copolymerization resin is added on and uses in the polyvinyl chloride (PVC) RESINS, the value of calculating by following formula.
Z＝X×Y÷100
Z: with vinyl chloride resin 100 weight parts is the content (weight part) of the macromonomer composition of benchmark
X: the macromonomer composition accounts for the branch rate (weight %) of whole vinyl chloride copolymer resins
Y: with respect to the interpolation umber (weight part) of the vinyl chloride copolymer resin of vinyl chloride resin 100 weight parts
* 2) impact toughener: the MBS resin
Vinyl chloride resin composition of the present invention, forming process become calendering goods such as blister pack goods, leatherware, agricultural film, shrinkable film, various sheet materials; Laminate film on the body materials such as vinyl chloride steel plates; Laminations such as laminate sheet material; Injection molded article such as joint, valve; Extrusion moulding bodies such as pipe, flat board, waved plate, film, band, sheet material, foaming plate or sheet, window frame, other special-shaped outlines; Blow molded articles such as bottle, conduit rubber case, corrugated tube; Various goods such as toy, billboard, mask, compacting base plate equal vacuum formed body use.
Claims (7)
1, vinyl chloride resin composition, it is characterized in that: the vinyl chloride copolymer resin is added in the vinyl chloride resin, described vinyl chloride copolymer resin obtains by making vinyl monomer and macromonomer copolymerization, and described macromonomer has the polymkeric substance that is made of the ethylenically unsaturated monomers that contains two keys on main chain.
2, the described vinyl chloride resin composition of claim 1 is characterized in that: with vinyl chloride resin 100 weight parts is benchmark, and the content of this macromonomer composition is 0.1～5 weight part.
3, each described vinyl chloride resin composition of claim 1～2 is characterized in that: in this vinyl chloride copolymer resin, this macromonomer composition accounts for 3～50 weight %.
4, formed body, it is formed by each described vinyl chloride resin composition of claim 1～3.
5, the described formed body of claim 4 is characterized in that: adopt rolling processing to make its moulding.
6, the described formed body of claim 4 is characterized in that: adopt injection molding to make its moulding.
7, the described formed body of claim 4 is characterized in that: adopt extrusion moulding to make its moulding.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004099103A JP2005281567A (en) | 2004-03-30 | 2004-03-30 | Vinyl chloride resin composition for calendering |
| JP099103/2004 | 2004-03-30 | ||
| JP099113/2004 | 2004-03-30 | ||
| JP099121/2004 | 2004-03-30 | ||
| JP099138/2004 | 2004-03-30 |
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| CN1922264A true CN1922264A (en) | 2007-02-28 |
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| CN 200580005715 Pending CN1922264A (en) | 2004-03-30 | 2005-03-16 | Vinyl chloride resin composition |
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| CN111234084A (en) * | 2020-01-10 | 2020-06-05 | 江苏利思德新材料有限公司 | Vinyl chloride copolymer emulsion for water-based anticorrosive paint and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2006103809A1 (en) * | 2005-03-25 | 2006-10-05 | Kaneka Corporation | Gamma-ray-resistant, flexible vinyl chloride molded article |
| WO2006103807A1 (en) * | 2005-03-25 | 2006-10-05 | Kaneka Corporation | Vinyl chloride sheet |
| WO2006103806A1 (en) * | 2005-03-25 | 2006-10-05 | Kaneka Corporation | Vinyl chloride copolymer resin composition and vinyl chloride injection molded article produced from the same |
| WO2006103808A1 (en) * | 2005-03-25 | 2006-10-05 | Kaneka Corporation | Stain-proof vinyl chloride film |
| JP2008156375A (en) * | 2005-03-31 | 2008-07-10 | Kaneka Corp | Vinyl chloride resin dope composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS6143645A (en) * | 1985-08-06 | 1986-03-03 | Kanegafuchi Chem Ind Co Ltd | Vinyl chloride resin composition containing vinyl chloride copolymer |
| US5120790A (en) * | 1987-05-07 | 1992-06-09 | The B. F. Goodrich Company | Blends of comb-shaped copolymers of a macromolecular monomer of polylactone with polymer (s) |
| US5247040A (en) * | 1991-06-27 | 1993-09-21 | Rohm And Haas Company | Graft copolymers prepared by two staged aqueous emulsion polymerization |
| JPH07126469A (en) * | 1993-11-05 | 1995-05-16 | Asahi Glass Co Ltd | Vinyl chloride-based resin composition |
| JPH10259282A (en) * | 1997-03-19 | 1998-09-29 | Shin Etsu Chem Co Ltd | Vinyl chloride-based resin composition |
| JP4643895B2 (en) * | 2002-06-28 | 2011-03-02 | 株式会社カネカ | Vinyl chloride copolymer resin for paste, composition and method for producing resin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234084A (en) * | 2020-01-10 | 2020-06-05 | 江苏利思德新材料有限公司 | Vinyl chloride copolymer emulsion for water-based anticorrosive paint and preparation method and application thereof |
| CN111234084B (en) * | 2020-01-10 | 2022-02-18 | 江苏利思德新材料有限公司 | Vinyl chloride copolymer emulsion for water-based anticorrosive paint and preparation method and application thereof |
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