CN101405138B - Multilayer sheet and molded article - Google Patents

Multilayer sheet and molded article Download PDF

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Publication number
CN101405138B
CN101405138B CN200780010276.6A CN200780010276A CN101405138B CN 101405138 B CN101405138 B CN 101405138B CN 200780010276 A CN200780010276 A CN 200780010276A CN 101405138 B CN101405138 B CN 101405138B
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component
quality
polymer
layer
polymerization
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CN101405138A (en
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马渡政明
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TAKANON RESIN CO Ltd
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TAKANON RESIN CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Disclosed is a multilayer sheet which is excellent in antistatic property, chemical resistance, impact resistance, surface appearance and vacuum formability. Specifically disclosed is a multilayer sheet comprising a layer of the component (A) described below and another layer of the component (B) described below. Component (A): an antistatic resin composition containing 7-91% by mass of an olefin resin (A-1); 5-50% by mass of a (co)polymer (A-2) of a vinyl monomer containing a rubber-reinforced styrene resin and/or an aromatic vinyl compound; 2-50% by mass of a block copolymer or a hydrogenated product thereof (A-3) which contains a polymer block of an aromatic vinyl compound and a polymer block of a conjugated diene compound; and 2-60% by mass of a block copolymer (A-4) containing an olefin polymer block and a hydrophilic polymer block Component (B): an olefin resin composition containing 60-97% by mass of a polypropylene resin (B-1) having a melt flow rate of not more than 2.0 g/10 min; and 3-40% by mass of a polyethylene resin (B-2) having a melt flow rate of not more than 2.0 g/10 min.

Description

Multi-layer sheet and mechanograph
Technical field
The present invention relates to excellent multi-layer sheet of antistatic behaviour, chemical-resistant, resistance to impact, appearance and vacuum formability and the mechanograph of processing by this multi-layer sheet.
Because vistanex for example polypropylene is superior at aspects such as chemical-resistant, hear resistance and flowabilities, so they are widely used for electric/electronic field, office automation (OA) and household appliance technical field, vehicular field, health field etc.Yet; Because these resins have their charged defectives easily; So they are difficult to use in the articles for use responsive to electrostatic breakdown, for example, LCD, plasma display, semi-conductive marginal portion and in various clean rooms, use or the parts handled, sheet material, film etc.In order to improve such defective, proposed the specific antistatic additive of blend in the patent document 1 and 2, but antistatic behaviour is not lasting, insufficient grade still is a problem.In addition,, proposed in the patent document 3, but shown that deficiently antistatic behaviour still is a problem particular polymers and vistanex blend as the method for keeping antistatic behaviour.
On the other hand; Because the styrene resin that rubber strengthens for example ABS resin resistance to impact, mouldability, mechanical strength for example rigidity etc. is excellent and also excellent aspect the appearance of mechanograph; So they are widely used for the electric/electronic field; Office automation (OA) and household appliance technical field, vehicular field, health field etc.Yet they are still not enough to some application aspect chemical-resistant, and therefore require the further improvement aspect chemical-resistant.In addition, this type of styrene resin has and above-mentioned similar electrostatic breakdown problem, and hopes improvement in this regard.Proposed in the patent document 4 polyamide elastomer and for example ABS resin blend of styrene resin, still still debatable is not show antistatic behaviour fully.
As the result who under said circumstances, furthers investigate; The material that has been found that excellent antistatic property can obtain through block copolymer that will have olefin polymer block and hydrophilic polymer block and the composition blend of being made up of vistanex and ABS resin, and is applied to patent (patent document 5).Yet, still have multi-layer sheet inadequate situation aspect vacuum formability of wherein using this material.
Patent document 1: Japanese Patent Laid open (Kokai) number H4-258647
Patent document 2: Japanese Patent Laid open (Kokai) number 2000-313875
Patent document 3: Japanese Patent Laid open (Kokai) number 2001-278985
Patent document 4: Japanese Patent Laid open (Kokai) number S60-23435
Patent document 5: Japanese Patent Laid open (Kokai) number 2005-154730
Summary of the invention
The problem that the present invention will solve
The purpose of this invention is to provide the excellent multi-layer sheet of antistatic behaviour, chemical-resistant, resistance to impact, appearance and vacuum formability.In addition, another object of the present invention provides the mechanograph of being processed by this multi-layer sheet.
The means of dealing with problems
In order to achieve the above object; The inventor furthers investigate; So finding the object of the invention can realize through the following multi-layer sheet that obtains: will be pressed onto layer by layer on the layer of forming by the composition that comprises specific acrylic resin and specific polyvinyl resin with specified quantitative by what specific anti-static resin composition was formed, thereby accomplished the present invention.
That is, according to the present invention, provide comprise at least by following component (A) form the layer and by following component (B) forms layer multi-layer sheet:
Component (A): the anti-static resin composition that comprises following component:
7-91 quality % (A-1) olefin resin;
The styrene resin that 5-50 quality % (A-2) strengthens through the rubber that in the presence of rubber-like polymer, makes the polymerization of vinyl monomer acquisition that comprises aromatic vinyl compound, and/or (being total to) polymer of said vinyl monomer;
At least a polymer of 2-50 quality % (A-3) is selected from the block copolymer that comprises mainly the polymer blocks is made up of aromatic vinyl compound and the main polymer blocks of being made up of conjugated diene compound, and hydrogenated products; With
2-60 quality % (A-4) comprises the block copolymer of olefin polymer block and hydrophilic polymer block, condition be said components (A-1), (A-2), (A-3) and summation (A-4) be 100 quality % and
Component (B): the olefin resin composition that comprises following component:
60-97 quality % (B-1) melt flow rate (MFR) (under 230 ℃ temperature, adopting the load measurement of 2.16kg according to JIS K7210:1999) is no more than the acrylic resin of 2.0g/10min; With
3-40 quality % (B-2) melt flow rate (MFR) (under 190 ℃ temperature, adopting the load measurement of 2.16kg according to JIS K6922-2) is no more than the polyvinyl resin of 2.0g/10min.
The layer of being made up of component (B) can foam.When requiring excellent antistatic property and have the outstanding foam multi-layer sheet of the sheet surface outward appearance of smooth surface; Preferred ingredient (A) is to comprise following component anti-static resin composition: 7-30 quality % olefin resin (A-1), 5-20 quality % (being total to) polymer (A-2), 15-50 quality % polymer (A-3) and 20-60 quality % block copolymer (A-4), condition are that component (A-1), (A-2), (A-3) and summation (A-4) are 100 quality %.
In addition, according to another aspect of the present invention, mechanograph is provided, has it is characterized in that by above-mentioned multi-layer sheet vacuum mo(u)lding.
Effect of the present invention
The invention provides multi-layer sheet, it is by constituting with lower floor: the layer of forming by above-mentioned specific anti-static resin composition and by the olefin resin composition that comprises acrylic resin with above-mentioned specific melt flow rate (MFR) and polyvinyl resin form layer.Therefore, can obtain the excellent sheet material of antistatic behaviour, chemical-resistant, resistance to impact, appearance and vacuum formability, and can be through above-mentioned multi-layer sheet vacuum mo(u)lding being obtained the mechanograph of above-mentioned excellent performance.
Preferred forms of the present invention
Hereinafter, will describe the present invention in detail.In this manual, term ＂ (being total to) polymer ＂ is meant homopolymers and copolymer, and term ＂ (methyl) acryloyl group ＂ is meant acryloyl group and/or methacryl, and term ＂ (methyl) acrylic acid ester ＂ is meant acrylic acid ester and/or methacrylate.
The olefin resin (A-1) of anti-static resin composition of the present invention (A) is the olefin resin that is made up of at least a alkene that is selected from the alkene that contains 2-10 carbon atom, and is (being total to) polymer of getting rid of the component of describing after a while (A-4).This olefin resin (A-1) can use or two kinds or the use of more kinds of combination ground individually.
The alkene that is used to prepare olefin resin (A-1) for example comprises that ethene and alpha-olefin be propylene, butene-1, amylene-1, hexene-1,3-methyl butene-1,4-methylpentene-1 and 3-methyl hexene-1 for example, and comprises for example ENB of cyclic olefin.They can use or two kinds or the use of more kinds of combination ground individually.In the middle of them, preferably ethene, propylene, butene-1,3-methyl butene-1,4-methylpentene-1 and ENB.
This other monomer that can randomly be used to prepare olefin resin (A-1) comprises for example 4-methyl isophthalic acid of non-conjugated diene, 4-hexadiene, 5-methyl isophthalic acid, 4-hexadiene, 7-methyl isophthalic acid, 6-octadiene and 1,9-decadinene.
The polymer that olefin resin (A-1) preferably mainly is made up of propylene units is polypropylene and propylene-ethylene copolymers, polyethylene and ethylene-norbornene conjugated polymer for example, and the especially preferably main polymer of being made up of propylene units for example polypropylene and propylene-ethylene copolymers.They can individually or combine ground to use.Simultaneously, aforesaid propylene-ethylene copolymer is random copolymer, block copolymer etc. preferably, and to the consideration of multi-layer sheet appearance random especially preferably.In addition, as polyethylene, can use in high density polyethylene (HDPE), low density polyethylene (LDPE), the LLDPE etc. any.
Be used for olefin resin of the present invention and can be through the known polymerization olefin resin of high pressure polymerization process, low-pressure polymerization method and the preparation of metallocene catalyst polymerization for example.
In addition, being used for olefin resin of the present invention can be the olefin resin that polymerization catalyst is gone catalysis, or with the olefin resin of modifications such as acid anhydrides, carboxyl, epoxy radicals.
As olefin resin (A-1), can use crystallization or amorphous olefin resin, but preferred use has at room temperature by what X-ray diffraction was measured and is no less than at least a in those of 10% crystalline olefin resin degree.
As olefin resin (A-1), what preferably use is to have the olefin resin of measuring according to JIS K7121 that is no less than 40 ℃ fusing point.
When using acrylic resin as component of the present invention (A-1); It should have preferred 0.01-500g/10min; More preferably 0.05-100g/10min's adopts the melt flow rate (MFR) of the load measurement of 2.16kg according to JIS K7210:1999 under 230 ℃ temperature; With when using polyvinyl resin, it should have preferred 0.01-500g/10min, more preferably the melt flow rate (MFR) according to the JISK6922-2 measurement of 0.05-100g/10min.
The amount to be used that constitutes the component (A-1) of component of the present invention (A) is 7-91 quality %; Preferred 10-85 quality %; More preferably 20-80 quality %, especially preferred 20-75 quality %, condition is that component among the present invention (A-1), (A-2), (A-3) and summation (A-4) they are 100 quality %.When requiring excellent antistatic property and have the outstanding foam multi-layer sheet of the sheet surface outward appearance of smooth surface, preferably this amount is 7-30 quality %.When this measured less than 7 quality %, resistance to impact, antistatic behaviour, chemical-resistant, appearance and vacuum formability were poor; When it surpasses 91 quality %, antistatic behaviour and poor impact resistance.
Component of the present invention (A-2) is the styrene resin that strengthens through the rubber that in the presence of rubber-like polymer (a), makes vinyl monomer (b) the polymerization acquisition that comprises aromatic vinyl compound, and/or (being total to) polymer of vinyl monomer (b).It should (being total to) polymer be compound through polyvinyl (b) polymerization that comprises aromatic vinyl compound is obtained.
From the consideration of impact intensity, preferred component of the present invention (A-2) comprises at least a through making vinyl monomer (b) glycerol polymerization obtain polymer in rubber-like polymer (a) existence.The content of rubber-like polymer (a) is 3-80 quality % preferably, more preferably 5-70 quality %, and especially preferred 10-60 quality %, condition is that component (A-2) is 100 quality %.
Above-mentioned rubber-like polymer (a) includes but not limited to the component (A-3) that polybutadiene, BS, hycar, ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene copolymer, ethene-1-Butylene copolymer, ethene-butene-1-non-conjugated diene copolymer, acrylic rubber, silicone rubber, silicone-acrylic resin IPN rubber and the latter describe, and they can use or two kinds or the use of more kinds of combination ground individually.
In the middle of them, the component (A-3) that polybutadiene, BS, ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene copolymer, acrylic rubber, silicone rubber and the latter describe is preferred.The BS of this use can block copolymer and random copolymer in any.
The gel content of above-mentioned rubber-like polymer (a) does not receive special restriction, but when obtaining component (a) through emulsion polymerisation, gel content preferably is no more than 98 quality %, more preferably 40-98 quality %.In this scope, can obtain to produce the anti-static resin composition of the excellent multi-layer sheet of resistance to impact.
Above-mentioned gel content can be measured through following method.That is, the 1g rubber-like polymer is added in the 100ml toluene, and allow this mixture at room temperature to leave standstill 48 hours.(quality definition is W to let this mixture filter 100 order metal screens then 1And weigh that (quality definition is W gram), and the toluene insoluble property material that should filter 80 ℃ of following vacuum drying and metal screen 6 hours, 2Gram).Gel content calculates through following formula (1).
Gel content (quality %)=[{ W 2(g)-W 1(g) }/1 (g)] * 100... (1)
Through during the preparation of rubber-like polymer, suitably adjusting the kind and the consumption of molecular weight improver, polymerization time, polymerization temperature, adjusting such as polymerisation conversion gel content.
The aromatic vinyl compound that constitutes above-mentioned vinyl monomer (b) comprises styrene, AMS, hydroxy styrenes etc.They can use or two kinds or the use of more kinds of combination ground individually.In the middle of them, styrene and AMS are preferred.
Can for example comprise acrylonitrile compound, (methyl) acrylate compounds, maleimide compound and the various unsaturated compound that contains other functional group with other vinyl monomer of aromatic vinyl compound combined polymerization.Vinyl monomer (b) preferably comprises aromatic vinyl compound as the basic monomer component; And comprise if necessary be selected from acrylonitrile compound, (methyl) acrylate compounds and the maleimide compound one or both or more as additional monomer component; And if further necessary, comprise the additional monomer component of at least a conduct in the various unsaturated compounds that contain other functional group.The various unsaturated compounds that contain other functional group for example comprise, the unsaturated compound of the unsaturated compound 、 Han oxazolinyl of unsaturated acids compound, the unsaturated compound that contains epoxy radicals, hydroxyl, contain the unsaturated compound of anhydride group and contain and replace or the unsaturated compound of unsubstituted amino.The various unsaturated compounds that contain other functional group can use or two kinds or the use of more kinds of combination ground individually.
Acrylonitrile compound in this use for example comprises, acrylonitrile and methacrylonitrile, and they can use or two kinds or the use of more kinds of combination ground individually.When using acrylonitrile compound, give chemical-resistant.When using acrylonitrile compound, its addition is with respect to component (b) preferably 1-60 quality %, more preferably 5-50 quality %.
(methyl) acrylate compounds for example comprises; Methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, EMA and butyl methacrylate, and they can use or two kinds or the use of more kinds of combination ground individually.
The use of (methyl) acrylate compounds improves case hardness, and is preferred therefore.When using (methyl) acrylate compounds, its addition is with respect to component (b) preferably 1-80 quality %, more preferably 5-80 quality %.
Maleimide compound comprises, for example, maleimide, N-phenylmaleimide and N-cyclohexyl maleimide, and they can use individually or two kinds or more kinds of combination ground use.In order to introduce the maleimide amine unit,, can carry out imidizate then at first with the maleic anhydride combined polymerization.When using maleimide compound, give hear resistance.When using maleimide compound, its amount to be used is with respect to component (b) preferably 1-60 quality %, more preferably 5-50 quality %.
The unsaturated acids compound for example comprises, acrylic acid, methacrylic acid, ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid and cinnamic acid, and they can use or two kinds or the use of more kinds of combination ground individually.
The unsaturated compound that contains epoxy radicals comprises, for example, glycidyl acrylate, GMA and allyl glycidyl ether, and they can use individually or two kinds or more kinds of combination ground use.
The unsaturated compound of hydroxyl for example comprises; 3-hydroxyl-1-propylene, 4-hydroxyl-1-butylene, cis-4-hydroxyl-2-butylene, trans-4-hydroxyl-2-butylene, 3-hydroxy-2-methyl-1-propylene, methacrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxyl ethyl ester and N-(4-hydroxyphenyl) maleimide, and they can use individually or two kinds or more kinds of combination ground use.
The unsaturated compound of Han oxazolinyl comprises, for example, Yi Xi oxazolin, and they can use individually or two kinds or more kinds of combination ground use.
The unsaturated compound that contains anhydride group for example comprises, maleic anhydride, itaconic anhydride and citraconic anhydride, and they can use or two kinds or the use of more kinds of combination ground individually.
The unsaturated compound that contains replacement or unsubstituted amino for example comprises; Acrylic acid ammonia ethyl ester, acrylic acid propyl group ammonia ethyl ester, dimethylaminoethyl acrylate methyl base ammonia ethyl ester, methacrylic acid phenylamino ethyl ester, N-vinyl diethylamine, N-acetyl group vinylamine, acryloyl group amine, methacryl amine, N-methacryl amine, acrylamide, N methacrylamide and p-aminophenyl ethene, and they can use or two kinds or the use of more kinds of combination ground individually.
When using the various unsaturated compound that contains other functional group, the blend of styrene resin and another kind of polymer will be improved aspect the two the compatibility.The preferred monomer that reaches a kind of like this effect is the unsaturated compound of the unsaturated compound, unsaturated acids compound and the hydroxyl that contain epoxy radicals.
The above-mentioned various to be used amount of unsaturated compound in component (A-2) that contains other functional group is with respect to component (A-2) 0.1-20 quality % preferably, and more preferably 0.1-10 quality % contains the total amount of the unsaturated compound of functional group by these.
The amount to be used of the monomer in the vinyl monomer (b) except that aromatic vinyl compound is 10-95 quality % preferably, more preferably 10-90 quality %, and especially preferred 15-80 quality %, condition is that the summation of vinyl monomer (b) is 100 quality %.The more preferably combination that constitutes the monomer of vinyl monomer (b) for example comprises; Styrene/acrylonitrile, styrene/methacrylic acid methyl esters, styrene/acrylonitrile/methyl methacrylate, styrene/acrylonitrile/GMA, styrene/acrylonitrile/methacrylic acid 2-hydroxyl ethyl ester, styrene/acrylonitrile/(methyl) acrylic acid, styrene/N-phenylmaleimide and styrene/methacrylic acid methyl esters/cyclohexyl maleimide, especially preferred combination is a styrene/acrylonitrile.The more preferably combination of treating monomer polymerized in the presence of rubber-like polymer (a) comprises styrene/acrylonitrile=65/45-90/10 (mass ratio), styrene/methacrylic acid methyl esters=80/20-20/80 (mass ratio) and styrene/acrylonitrile/methyl methacrylate; Wherein cinnamic amount is 20-80 quality %; The amount of the summation of acrylonitrile and methyl methacrylate is 20-80 quality %, and especially preferred combination is styrene/acrylonitrile=70/30-85/15 (mass ratio).
Component of the present invention (A-2) can be through the polymerization preparation of the for example emulsion polymerisation of known polymerization, polymerisation in bulk, polymerisation in solution, suspension polymerisation and their combination.In the middle of them, be emulsion polymerisation and polymerisation in solution through the preferred polymerization that in the presence of rubber-like polymer (a), makes the polymer that vinyl monomer (b) (being total to) polymerization obtains.On the other hand, be polymerisation in bulk, polymerisation in solution, suspension polymerisation and emulsion polymerisation through the preferred polymerization that under the situation that does not have rubber-like polymer (a), makes the polymer that vinyl monomer (b) (being total to) polymerization obtains.
When producing, use polymerization initiator, chain-transferring agent, emulsifying agent etc., and all these can be usually known those through emulsion polymerisation.
Polymerization initiator for example comprises that cumene hydroperoxide, hydroperoxidation are to terpane, hydroperoxidation diisopropyl benzene, hydroperoxidation tetramethyl butyl, t-butyl hydroperoxide, potassium peroxydisulfate and azodiisobutyronitrile.
In addition, cause auxiliary agent, preferably use the for example various reducing agents of redox system, contain sugared ferric pyrophosphate prescription and sulfoxylate prescription as polymerization.
Chain-transferring agent comprises that for example, mercaptan is octyl mercaptan, n-dodecyl mercaptan, uncle's lauryl mercaptan, n-hexyl mercaptan, terpinolene and AMS dimer for example.
Emulsifying agent comprises that for example, alkylbenzenesulfonate is neopelex for example, and aliphatic sulfonate is NaLS for example, and higher fatty acid salt is potassium laurate, potassium stearate, potassium oleate and potassium palmitate and rosinate resin acid potassium for example for example.
As for the mode that rubber-like polymer (a) and vinyl monomer (b) is used for emulsion polymerisation, can fully add vinyl monomer (b) and polymerization in the presence of total amount rubber-like polymer (a), or can be dividually or add continuously and polymerization.In addition, can in polymerization process, add a part of rubber-like polymer (a).
After emulsion polymerisation, the latex and the coagulating agent that are obtained are condensed, then with water washing and dry and obtain the powder of component of the present invention (A-2).During this time, can condense then suitably with two kinds or more kinds of latex blend of the component (A-2) that obtains through emulsion polymerisation.Comprise for example for example sulfuric acid, hydrochloric acid, acetate, citric acid and malic acid of calcium chloride, magnesium sulfate and magnesium chloride and acid of inorganic salts at the coagulating agent of this use.
Operable solvent is the solvent to the polymerization inertia when through solution polymerization component (A-2), and they are used for common radical polymerization.Their instance comprises aromatic hydrocarbon for example ethylo benzene and toluene, and ketone is methyl ethyl ketone and acetone for example, acetonitrile, dimethyl formamide, N-methyl pyrrolidone etc.
Polymerization temperature is preferably 80-140 ℃, more preferably 85-120 ℃.Between polymerization period, can use polymerization initiator, perhaps can under the situation of not using any polymerization initiator, carry out polymerization through thermal polymerization.The preferred polymerization initiator that uses for example comprises, organic peroxide for example ketone peroxide, dialkyl, peroxidating two acyls, peroxyester, hydroperoxides, azodiisobutyronitrile, benzoyl peroxide and 1,1 '-azo two (cyclohexane-1-nitrile).
In addition, when using chain-transferring agent, it for example can be, mercaptan, terpenolenes and α-Jia Jibenyixierjuwu.
When producing, can use the polymerization initiator that relates to polymerisation in solution and describe, chain-transferring agent etc. through polymerisation in bulk or suspension polymerisation.
The amount of remaining monomer preferably is no more than 10 in the component (A-2) through above-mentioned corresponding polymerization acquisition, and 000ppm further preferably is no more than 5,000ppm.
Generally include the component that this graft copolymerization of vinyl monomer wherein is incorporated into the copolymer on this rubber-like polymer and does not have grafting through the polymers compositions that in the presence of rubber-like polymer (a), vinyl monomer (b) polymerization is obtained, this component that does not have a grafting by this vinyl monomer manufacturing but be not grafted to ((being total to) polymer of above-mentioned vinyl monomer (b)) on this rubber-like polymer.
The percent grafting of said components (A-2) is 20-200 quality % preferably, further preferred 30-150 quality %, and especially preferred 40-120 quality %, and this percent grafting can be confirmed through following formula (2).
Percent grafting (quality %)=(T-S)/S} * 100... (2)
In the above-mentioned formula (2); T is the quality (g) of the following insoluble substance that obtains: add 1g component (A-2) to 20ml acetone (when in rubber-like polymer (a), using acrylic rubber; But acetonitrile) in, shook this mixture 2 hours, pass through centrifuge then (with 23 through shaking machine; The rotating speed of 000rpm) centrifugalize this mixture 60 minutes with separatin non-soluble material and solable matter, S is the quality (g) of the rubber-like polymer that comprises in the 1g component (A-2).
The solable matter of component of the present invention (A-2) at acetone (when in rubber-like polymer (a), using acrylic rubber; But acetonitrile) inherent viscosity in [η] (using methyl ethyl ketone to measure down at 30 ℃ as solvent) is 0.2-1.2dl/g preferably; Further preferred 0.2-1.0dl/g, especially preferred 0.3-0.8dl/g.
Be dispersed in the average grain diameter 500-30 preferably of the rubber-like polymer particle of the grafting in the component (A-2), 000 dust, further preferred 1,000-20,000 dust, especially preferred 1,500-8,000 dust.Can use electron microscope to measure average grain diameter through conventional method.
The amount to be used that constitutes the component (A-2) of component of the present invention (A) is 5-50 quality %; Preferred 7-50 quality %; Further preferred 7-38 quality %, especially preferred 10-30 quality %, condition is that component of the present invention (A-1), (A-2), (A-3) and summation (A-4) they are 100 quality %.When requiring excellent antistatic property and have the outstanding foam multi-layer sheet of the sheet surface outward appearance of smooth surface, preferably this amount is 5-20 quality %.When this measured less than 5 quality %, antistatic behaviour, resistance to impact and appearance were poor; When it surpasses 50 quality %, chemical-resistant is poor.
Component of the present invention (A-3) is to be selected from the block copolymer (A-3-a) that comprises polymer blocks (A-3-1) and polymer blocks (A-3-2); At least a polymer with its hydrogenated products (A-3-b); This polymer blocks (A-3-1) mainly is made up of aromatic vinyl compound, and this polymer blocks (A-3-2) mainly is made up of conjugated diene compound.
Aromatic vinyl compound in this use for example comprises, styrene, AMS and hydroxy styrenes.In the middle of them, styrene and/or AMS are preferred, and styrene is especially preferred.Conjugated diene compound comprises, for example, butadiene, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene and 1,3-pentadiene preferably include butadiene and isoprene.They can use or two kinds or the use of more kinds of combination ground individually.In addition, block (A-3-2) can comprise two kinds or more kinds of conjugated diene compound, and they can be by random, block or tapered form keyed jointing.Block (A-3-2) can also comprise 1-10 tapered; Wherein the content of aromatic vinyl compound increases gradually; Maybe can also be the copolymer that comprises vinyl bonds content different polymer block, this vinyl bonds be derived from the conjugated diene compound of polymer blocks (A-3-2).
The preferred construction of component of the present invention (A-3) is by the polymer of following general formula (I)-(III) expression or their hydrogenation products.
(A-B) Y (I)
(A-B) Y-X (II)
A-(B-A) Z (III)
(in general structure (I)-(III), the A representative has the polymer blocks of aromatic vinyl compound as major constituent, and can partly comprise conjugated diene compound, as long as it is the polymer blocks of being made up of aromatic vinyl compound basically.Preferably, A comprises to be no less than 90 quality %, more preferably is no less than the polymer blocks of 99 quality % aromatic vinyl compounds.B represents the homopolymers of conjugated diene compound, or conjugated diene compound and the another kind of monomer copolymer of aromatic vinyl compound for example.X represents the residue of coupling agent, and Y representes the integer of 1-5, and Z representes the integer of 1-5.)
The ratio of aromatic vinyl compound and conjugated diene compound that is ready to use in component of the present invention (A-3) is preferably at aromatic vinyl compound/conjugated diene compound=10-70/30-90 quality %; Further 15-65/35-85 quality % preferably is in the scope of especially preferred 20-60/40-80 quality %.
The block copolymer that comprises aromatic vinyl compound and conjugated diene compound is known in the technical field of anionic polymerisation; And, disclose among Japan Patent open (Kokoku) number S47-28915, S47-3252, S48-2423 and the S48-20038 for example.The preparation method of polymer blocks with tapered discloses among Japanese Patent Laid open (Kokai) number S60-81217 for example.
Derived from the content of the vinyl bonds (1,2-and 3,4-key) of the conjugated diene compound of component of the present invention (A-3) preferably in the scope of 5-80%.The number-average molecular weight of component of the present invention (A-3) preferably 10,000-1,000,000, more preferably 20,000-500,000, especially preferred 20,000-200,000.In the middle of them, the number-average molecular weight of A in general formula (I)-(III) part is preferably 3,000-150, and in 000 the scope, the number-average molecular weight of B part is preferably 5, and 000-200 is in 000 the scope.
The adjusting of the vinyl bonds content of conjugated diene compound can use following material to carry out: amine is N for example, N, N '; N '-tetramethylethylenediamine, trimethylamine, triethylamine, two azo rings (2,2,2) octylame etc.; Ether is oxolane, diethylene glycol dimethyl ether, diethylene glycol dibutyl ethers etc. for example, thioether, phosphine; Phosphamide, benzene sulfonamide acid esters, the alkoxide of potassium and sodium etc.
The another kind of preferred examples of component of the present invention (A-3) comprises through said method and obtains and have residue prolongation or branched polymers chain via coupling agent with the polymer of coupling agent treatment so that it.Can comprise diethylene adipate, divinylbenzene, dimethyl dichlorosilane (DMCS), silicon tetrachloride, butyl trichlorosilicane, butter of tin, butyl tin trichloride, dimethyl chlorination silicon, germanium tetrachloride, 1 at the instance of the coupling agent of this use; 2-Bromofume, 1; 4-chloromethylbenzene, two (silicochloroform base) ethane, epoxidised Linseed oil, toluylene group diisocyanate, 1; 2,4-benzene triisocyanate etc.
In the middle of above-mentioned block copolymer; Preferably those are the polymer with block (A-3-2) from resistance to impact is considered; And/or having experienced the radially block type polymer of coupling processing, this block (A-3-2) comprises 1-10 the wherein tapered that increase gradually of aromatic vinyl compound.
In addition, as component (A-3), the carbon-to-carbon double bond that not only can use above-mentioned block copolymer itself but also can use the part of conjugated diene wherein is those of hydrogenation partially or completely.From consideration to the low temperature resistance to impact of the composition that obtained, preferably use unhydrided those with hydrogenating rate less than 90% those.From consideration to the weatherability (light resistance) of the composition that obtained, preferably use hydrogenating rate be no less than 90% those.
Obtain and the hydrogenation that comprises mainly the polymer blocks is made up of aromatic vinyl compound and the block copolymer of the main polymer blocks of being made up of conjugated diene compound can carry out through known method through said method.In addition, can regulate hydrogenating rate through known method and obtain required polymer.Concrete method comprises open (Kokoku) number S42-8704 of Japan Patent, S43-6636, S63-4841 and S63-5401 and open (Kokai) number H2-133406 of Japanese Patent Laid and H1-297413.
Can another kind of polymer be chemically bonded on above-mentioned block copolymer (A-3-a) and its hydrogenated compound (A-3-b) as block polymer and/or graft polymers (getting rid of said components (A-2)).
The above-mentioned another kind of polymer of 100 (100) percentage not necessarily is chemically bonded on above-mentioned block copolymer (A-3-a) and its hydrogenated compound (A-3-b), and when the above-mentioned another kind of polymer chemistry keyed jointing of at least 10 quality %, the object of the invention can be realized.
Be keyed to above-mentioned another kind of polymer preferably aromatic polycarbonate and/or polyurethane on above-mentioned block copolymer (A-3-a) and its hydrogenated compound (A-3-b) as block polymer, further preferred aromatic polycarbonate.Can for example pass through, the method for describing among Japanese Patent Laid open (Kokai) number 2001-220506 prepares aromatic polycarbonate block copolymer/mixture.In addition, it for example can be used as, Kuraray Co., and the TM-S4L77 and the TM-H4L77 (trade name) of the TM series of polymers of Ltd. preparation obtain.
In addition, the especially preferred method that above-mentioned another kind of polymer graft is aggregated on above-mentioned block copolymer (A-3-a) and its hydrogenated compound (A-3-b) is with the vinyl monomer-grafted polymerization in the presence of above-mentioned block copolymer (A-3-a) and its hydrogenated compound (A-3-b).As vinyl monomer, preferably use the vinyl monomer (b) (it can be identical or different with the compound of use in the component (A-2)) of component (A-2).Graft polymerization procedure can be any in above-mentioned emulsion polymerization, polymerisation in solution, polymerisation in bulk, the suspension polymerisation etc., and preferably polymerisation in solution and polymerisation in bulk.
Component of the present invention (A-3) is pressed 2-50 quality %, preferred 5-45 quality %, and further preferred 7-40 quality %, the amount of especially preferred 10-35 quality % is used, and condition is that component (A-1), (A-2), (A-3) and the summation (A-4) among the present invention is 100 quality %.When requiring excellent antistatic property and have the outstanding foam multi-layer sheet of the sheet surface outward appearance of smooth surface, this measures preferably 15-50 quality %.When it during less than 2 quality %, poor impact resistance; When it surpasses 50 quality %, resistance to impact and sheet surface appearance poor.
Component of the present invention (A-4) is the block copolymer that comprises olefin polymer block (A-4-1) and hydrophilic polymer block (A-4-2), and can be diblock, maybe can be three or many blocks of more blocks.Olefin polymer block (A-4-1) is (being total to) polymer of alkene.Alkene in this use for example comprises; Ethene and alpha-olefin be propylene, butene-1, hexene-1,3-methyl butene-1,4-methylpentene-1 and 3-methyl hexene-1 for example; And comprise for example ENB of cyclic olefin, optimal ethylene, propylene, butene-1,3-methyl butene-1,4-methylpentene-1 and ENB.In addition, non-conjugated diene is the 4-methyl isophthalic acid for example, 4-hexadiene, 5-methyl isophthalic acid, and 4-hexadiene, 7-methyl isophthalic acid, 6-octadiene and 1, the 9-decadinene can be as the part of this polymers compositions.The number-average molecular weight of olefin polymer block (A-4-1) is 800-20 preferably, and 000, more preferably 1,000-10,000, especially preferred 1,200-6,000, (GPC) measures and changes into the polystyrene equivalent by gel permeation chromatography.
Above-mentioned block (A-4-1) is chemically bonded on the above-mentioned block (A-4-2).They are via at least a keyed jointing that is selected from ester bond, amido link, ehter bond, urethane bond, the imide bond etc.Wherein they press the structure of alternately repeated mode via these key keyed jointings in this block formation.Yet the block of keyed jointing can almost not have effect to comprise to the antistatic behaviour of mentioning after a while with them.
Therefore, the molecular end of above-mentioned block (A-4-1) must be by functional group modification, this functional group can with the functional group reactions of two molecular ends of above-mentioned block (A-4-2).These functional groups for example comprise, carboxyl, hydroxyl, amino, anhydride group 、 oxazolinyl, epoxy radicals etc.
The method for optimizing of giving these functional groups is that the carbon carbon unsaturated compound that wherein will have an above-mentioned functional group adds at its molecular end and has the method on the thermal degradation component (A-4-1) of carbon-to-carbon double bond.
The hydrophilic polymer of above-mentioned block component (A-4-2) for example comprises, polyethers, the hydrophilic polymer that contains polyethers and anionic polymer.
Polyethers comprises polyether Glycols, polyether diamine and its modified product.
The hydrophilic polymer that contains polyethers comprises the polyether ester amides with polyether Glycols segment, the polyetheramides acid imide with polyether Glycols segment, the polyether ester with polyether Glycols segment, have the polyetheramides of polyether diamine segment, have the polyethers urea alkane of polyether Glycols or polyether diamine segment.
Anionic polymer comprises and contains dicarboxylic acids with sulfonyl anionic polymer as main composition unit and polyethers, and preferably in its molecule, has 2-80 sulfonyl, more preferably 3-60 sulfonyl.They can be linearity or branching.Especially preferred component (A-4-2) is a polyethers.
Polyether Glycols as polyethers for example comprises, by those of general formula (IV) expression:
H-(OA 1) n-O-E 1-O(A 1O) n′-H
With by those of general formula (V) expression:
H-(OA 2) m-O-E 2-O-(A 2O) m′-H.
In general formula (IV), E 1Representative is removed hydroxyl and the residue that produces from the compound that contains dihydroxylic, A 1Be the alkylidene that contains 2-4 carbon atom, n and n ' represent with respect to contain the number of oxyalkylene of hydroxyl institute addition of the compound of dihydroxylic separately.(OA 1) n unit and A 1O) the individual unit of n ' can be identical or different, and when they are made up of two or more oxyalkylene groups, and this group can be by the mode keyed jointing of block, random or its combination.Normally, n and n ' are general 1-300, preferred 2-250, the integer of especially preferred 10-100.In addition, n and n ' can be identical or different.
The above-mentioned compound that contains dihydroxylic comprises the compound that contains two alcohol or phenolic hydroxyl group in the molecule; It is dihydroxy compounds; Particularly including dihydroxylic alcohols (aliphatic series, alicyclic ring and the aromatic diol that for example, contain 2-12 carbon atom), contain the dihydric phenol of 6-18 carbon atom and the dihydroxylic alcohols of tertiary-amino-containing.
The instance of aliphatic dihydric alcohol comprises aklylene glycol for example ethylene glycol and propane diols, 1,4-butanediol, 1,6-hexylene glycol, neopentyl glycol, 1,12-dodecanediol etc.
The instance of alicyclic ring dihydroxylic alcohols comprises 1,2-and 1, and 3-encircles pentanediol, 1,2-, 1,3-and 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol.The instance of aromatic diol comprises benzene dimethanol etc.
The instance of dihydric phenol comprises monocycle dihydric phenol for example quinhydrones, catechol, resorcinol and laccol, and bis-phenol is bisphenol-A, Bisphenol F, bisphenol S for example, 4; 4 '-dihydroxy diphenyl-2; The 2-butane, dihydroxybiphenyl, dihydroxy diphenyl ether and fused polycycle dihydric phenol be dihydroxy naphthalene and dinaphthol for example.
In general formula (V), E 2The residue that representative produces from removing hydroxyl like the compound of mentioning the general formula (IV) that contains dihydroxylic, A 2Be substituted alkylidene, its at least a portion is represented by general formula (VI) :-CHR-CHR '-[wherein one of R and R ' are the group by general formula (VII) expression :-CH 2O (A 3O) xR ' ', other is H, and in general formula (VII), x is the integer of 1-10, and R ' ' is H or alkyl, aryl, alkaryl, aralkyl or the acyl group that contains 1-10 carbon atom, A 3Be the alkylidene that contains 2-4 carbon atom], remaining A of while 2It can be the alkylidene that contains 2-4 carbon atom.(OA 2) m unit and (A 2O) m ' unit can be identical or different.Preferably, m and m ' are 1-300, further preferred 2-250, the integer of especially preferred 10-100.In addition, m and m ' can be identical or different.
Polyether Glycols by above-mentioned general formula (IV) expression can be through preparing the oxyalkylene addition reaction to the compound that contains dihydroxylic.As oxyalkylene, use the oxyalkylene that contains 2-4 carbon atom, for example comprise ethylene oxide, propylene oxide, oxidation 1,2-butylene, oxidation 1,4-butylene, oxidation 2,3-butylene and oxidation 1,3-butylene, and two kinds or more kinds of combinations in them.When two kinds of uses or more kinds of oxyalkylene, they can be by any keyed jointing in random and/or the block fashion.Preferred oxyalkylene be independent ethylene oxide and ethylene oxide with can be by the combination of the another kind of oxyalkylene of block and/or random fashion addition.The number of treating the oxyalkylene of addition is a preferred 1-300 of hydroxyl who contains the compound of dihydroxylic with respect to above-mentioned, more preferably 2-250, the especially preferably integer of 10-100.
Preferred embodiment by the preparation method of the polyether Glycols of above-mentioned general formula (V) expression comprises following method (1) and (2).
(1) wherein with the above-mentioned compound that contains dihydroxylic as parent material and glycidol ether polymerization by general formula (VIII) expression:
Figure G2007800102766D00181
[in general formula (VIII), A 4Be the alkylidene that contains 2-4 carbon atom, p is the integer of 1-10, R 1Be H or the alkyl that contains 1-10 carbon atom, aryl, alkaryl, aralkyl or acyl group], and randomly with the method for the oxyalkylene combined polymerization that contains 2-4 carbon atom.
(2) wherein use the compound that contains dihydroxylic to prepare the method for polyether Glycols via the polyethers that on side chain, contains the chloro methyl as parent material.More particularly; Addition copolymerization through chloropropylene oxide or chloropropylene oxide and oxyalkylene obtains on side chain, to contain the polyethers of chloro methyl, is prepared as follows this polyether Glycols then: the polyethers of acquisition and contain the PAG and the R of 2-4 carbon atom above under alkali, making 1X (R wherein 1As stated; X represents chlorine, bromine or iodine) reaction, or polyethers that obtains above in the presence of alkali, making and the polyalkylene glycol mono carboxyl ether reaction that contains 2-4 carbon atom.
As the oxyalkylene of treating in this use that contains 2-4 carbon atom, can use above-mentioned owning.
Preferred ingredients (A-4) can obtain above-mentioned olefin polymer block (A-4-1) and above-mentioned hydrophilic polymer block (A-4-2) polymerization through conventional method.For example, it can prepare through the polymerisation of under 200-250 ℃, under reduced pressure carrying out polymer blocks (A-4-1) and polymer blocks (A-4-2).In addition, can during polymerisation, use conventional polymerization catalyst.
Operable conventional polymerization catalyst preferably is selected from one or both or the more kinds of combinations in the following catalyst during polymerisation: tin-based catalyst is oxidation monobutyl tin for example; Antimony-based catalyst is antimony trioxide and antimony trichloride for example; Ti-base catalyst is butyl titanate for example; Zirconium-base catalyst is zirconium hydroxide, zirconia and zirconium acetate and IIB family acylate catalyst for example.
Be devoted to improved antistatic behaviour in order further to improve the present invention, can the salt (C) of alkali metal and/or alkaline-earth metal be introduced component (A-4).This component can be before the polymerization of component (A-4), introduces wherein between the polymerization period of component (A-4) or after the polymerization of component (A-4).In addition, this component (C) also can be introduced during the preparation according to anti-static resin composition of the present invention, or introduces by the mode that wherein said method is combined.
Component (C) comprises and the salt of organic acid, sulfonic acid or inorganic acid and alkali metal lithium, sodium and potassium and/or the alkaline-earth metal halide of magnesium and calcium for example for example.
The concrete preferred embodiment of component (C) comprises alkali-metal halide for example lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide and KBr; Alkali-metal inorganic acid salt is lithium perchlorate, sodium perchlorate and potassium hyperchlorate for example; Alkali-metal acylate is potassium acetate and lithium stearate for example; Alkyl sulfonic acid with the alkyl that contains 8-24 carbon atom is the alkali metal salt of octyl group sulfonic acid, dodecyl sodium sulfonate, myristyl sulfonic acid, octadecyl sulfonic acid, tetracosyl sulfonic acid and 2-ethylhexyl sulfonic acid for example; Aromatic sulfonic acid is the alkali metal salt of phenylbenzimidazole sulfonic acid and naphthyl sulfonic acid for example; Alkyl benzene sulphonate with the alkyl that contains 6-18 carbon atom is the alkali metal salt of octyl group benzene sulfonic acid, DBSA, dibutyl benzene sulfonic acid and dinonyl benzene sulfonic acid for example; Alkyl naphthalene sulfonic acid with the alkyl that contains 2-18 carbon atom is the alkali metal salt of dimethyl naphthyl sulfonic acid, diisopropyl naphthyl sulfonic acid and dibutyl naphthyl sulfonic acid for example; Fluorinated sulfonic is the alkali metal salt etc. of trifluoromethane sulfonic acid for example.They can use or two kinds or the use of more kinds of combination ground individually.With respect to component of the present invention (A-4), said components (C) can be used in the scope of further preferred 0.01-5 quality % at preferred 0.001-10 quality %.
The ratio of component (A-4-1) in the component of the present invention (A-4)/component (A-4-2) is 10-90/10-90 quality % preferably, further preferred 20-80/20-80 quality %, especially preferred 30-70/30-70 quality %.
These block copolymers (A-4) can for example pass through, the method preparation of mentioning among open (Kokai) number 2003-48990 of Japanese Patent Laid open (Kokai) number 2001-278985 and Japanese Patent Laid.Component of the present invention (A-4) also can be used as Sanyo ChemicalIndustries, and 230 and 201 of the ＂ PELESTAT ＂ 300 of 300 series of Ltd. preparation and 303 and 200 series obtain.
Said components among the present invention (A-4) is pressed the amount of 2-60 quality % and is used, and condition is that component (A-1), (A-2), (A-3) and summation (A-4) are 100 quality %.When this measured less than 2 quality %, antistatic behaviour was poor; When this amount surpasses 60 quality %, antistatic behaviour and sheet surface appearance poor.For the excellent chemical moral character that requires mechanograph and the application of appearance; Component of the present invention (A-4) is with preferred 2-40 quality %; More preferably 3-35 quality %; Further more preferably 5-35 quality %, the amount of especially preferred 5-30 quality % is used, and condition is that component (A-1), (A-2), (A-3) and summation (A-4) they are 100 quality %.For requiring the electrostatic application of excellent anti; Component of the present invention (A-4) is with preferred 12-60 quality %; More preferably 20-60 quality %; Further more preferably 30-60 quality %, the amount of especially preferred 35-60 quality % is used, and condition is that component (A-1), (A-2), (A-3) and summation (A-4) they are 100 quality %.
The melt flow rate (MFR) of the anti-static resin composition of component of the present invention (A) (under 230 ℃ temperature, adopting the load measurement of 2.16kg according to JISK7210:1999) is 0.5-25g/10min preferably; Further preferred 0.5-20g/10min, especially preferred 1.0-15g/10min.In this scope, antistatic behaviour, sheet surface outward appearance and resistance to impact are excellent.The melt flow rate (MFR) of component (A) can wait and change through change component (A-1), (A-2), (A-3) or molecular weight (A-4), composition.
The olefin resin composition of component of the present invention (B) comprises melt flow rate (MFR) (according to the load measurement of JISK7210:1999 at employing 2.16kg under 230 ℃ the temperature) and is no more than the acrylic resin (B-1) of 2.0g/10min and the polyvinyl resin (B-2) that melt flow rate (MFR) (under 190 ℃ temperature, adopting the load measurement of 2.16kg according to JIS K6922-2) is no more than 2.0g/10min.
Acrylic resin (B-1) in this use comprises the homopolymers of propylene and the copolymer of propylene and another kind of monomer.Above-mentioned another kind of monomer in this use comprises ethene, butene-1, amylene-1, hexene-1,3-methyl butene-1,4-methylpentene-1 and 3-methyl hexene-1, especially optimal ethylene.
Propylene-ethylene copolymers comprises random copolymer and block copolymer, and can use in them any.The amount of the monomer except that propylene of formation acrylic resin (B-1) is the 0-60 quality % of acrylic resin (B-1) total amount preferably.
The especially preferably even type polypropylene of the acrylic resin of the component of using among the present invention (B-1).
Component (B-1) under 230 ℃ temperature, to adopt the melt flow rate (MFR) of the load measurement of 2.16kg according to JIS K7210:1999 be 2.0g/10min or lower; Preferred 0.05-1.5g/10min; Further preferred 0.1-1.4g/10min, especially preferred 0.3-1.0g/10min.When it surpasses 2.0g/10min, the vacuum formability of multi-layer sheet of the present invention is poor.
Be used for polyvinyl resin of the present invention (B-2) and comprise the homopolymers of ethene and the copolymer of ethene and another kind of monomer.Above-mentioned another kind of monomer in this use comprises butene-1, amylene-1, hexene-1,3-methyl butene-1,4-methylpentene-1,3-methyl hexene-1, ENB etc.
As being used for polyvinyl resin of the present invention, the homopolymers of ethene is especially preferred.Though any in high density polyethylene (HDPE), low density polyethylene (LDPE) and the LLDPE can be used as polyethylene, starting from especially preferred to the consideration of vacuum formability is low density polyethylene (LDPE).
Component (B-2) under 190 ℃ temperature, to adopt the melt flow rate (MFR) of the load measurement of 2.16kg according to JIS K6922-2 be 2.0g/10min or lower; Preferred 0.05-1.5g/10min; Further preferred 0.1-1.2g/10min, especially preferred 0.3-1.0g/10min.When it surpasses 2.0g/10min, the vacuum formability of multi-layer sheet of the present invention is poor.
Olefin resin composition of the present invention (B) comprises component (B-1) and component (B-2); And amount to be used is component (B-1)/component (B-2)=60-97/3-40 quality %; Preferred 70-95/5-30 quality %, further preferred 70-90/10-30 quality %, especially preferred 75-90/10-25 quality %.Component (B-1) accounts for less than 60 quality % and component (B-2) and accounts in the scope greater than 40 quality % therein, and sheet material outward appearance and vacuum formability are poor.In addition, component (B-1) accounts for greater than 97 quality % and component (B-2) and accounts in the scope less than 3 quality % therein, and vacuum formability is poor.
In order further to improve the antistatic behaviour of component of the present invention (A), can during the preparation of component (A), add specific compound, and comprise lithium salt compound and non-ionic antistatic agent at the specific compound of this use.
The preferred lithium salt compound that uses comprises lithium perchlorate, trifluoromethayl sulfonic acid lithium, two (trifluoromethane sulfonyl group) imide li and three (trifluoromethane sulfonyl group) methane lithium, further preferred trifluoromethayl sulfonic acid lithium.They can use or two kinds or the use of more kinds of combination ground individually.They can be used as the Co. by Sanko Chemical, and the SANKONOL 0862-13T of Ltd. preparation, AQ-50T, AQ-75T, TBX-25 (trade name) obtain with solution or master batch form.This lithium salt compound can be used as said components (C).
With respect to 100 mass parts component of the present invention (A), lithium salt compound is preferably with the 0.01-5 mass parts, further preferred 0.1-3 mass parts, and especially preferred 0.3-2 mass parts is used.When its amount to be used during less than 0.01 mass parts, be unreachable to the improvement effect of antistatic behaviour, when it surpassed 5 mass parts, resistance to impact was tended to reduce.
Non-ionic antistatic agent for example comprises, polyol ester, amine and acid amides.The instance of polyol ester for example comprises; Glycerin monostearate, single myristin, monopalmitin, glycerin monostearate, single mountain acid glyceride, glyceryl monooleate, mono laurate two glyceride, single myristic acid two glyceride, single palmitic acid two glyceride, monostearate two glyceride, single mountain acid two glyceride, single oleic acid two glyceride, mono laurate Isosorbide Dinitrate, single myristic acid Isosorbide Dinitrate, single palmitic acid Isosorbide Dinitrate, monostearate Isosorbide Dinitrate, single mountain acid Isosorbide Dinitrate and mono laurate Isosorbide Dinitrate, and they can use or two kinds or the use of more kinds of combination ground individually.Especially preferred is glycerin monostearate, monostearate two glyceride, glyceryl monolaurate, mono laurate two glyceride, monostearate Isosorbide Dinitrate and the material that comprises at least 20 these materials of quality %.
Amine and acid amides comprise; For example; Amines is lauryl diethanol amine, myristyl diethanol amine, palmityl diethanol amine, octadecyldiethanol amine, oleyl diethanol amine, lauryl diisopropanolamine (DIPA), myristyl diisopropanolamine (DIPA), palmityl diisopropanolamine (DIPA), octadecyl diisopropanolamine (DIPA), oleyl diisopropanolamine (DIPA) and N for example; Two hydroxyethyl alkylamines (its alkyl contains 12-22 carbon atom) of N-and amide compound be lauryl diglycollic amide, myristyl diglycollic amide, palmityl diglycollic amide, docosyl diglycollic amide, oleyl diglycollic amide, lauryl diisopropanol acid amides, myristyl diisopropanol acid amides, palmityl diisopropanol acid amides, octadecyl diisopropanol acid amides and oleyl diisopropanol acid amides for example.They can use or two kinds or the use of more kinds of combination ground individually.Preferred what use is above-mentioned amines, further preferably comprises in 20 quality % lauryl diethanol amine and the octadecyldiethanol amine material of each at least.
In order to improve the antistatic behaviour of above-claimed cpd, can the blend conventional additives.Their instance comprises the higher alcohol that contains 12-18 carbon atom, lubricant, silica and calcium silicates.In order to improve miscibility, can use those that make masterbatch.
Above-mentioned non-ionic antistatic agent is commercially available, comprises ELECTROSTRIPPER EA, TS-3B, TS-6B, TS-5, TS-2B (trade name) by Kao Corporation preparation.
With respect to 100 mass parts component of the present invention (A), above-mentioned non-ionic antistatic agent is preferably with the 0.01-10 mass parts, further preferred 0.1-8 mass parts, and especially preferred 0.1-5 mass parts is used.When its amount to be used during less than 0.01 mass parts, be unreachable to the improvement effect of antistatic behaviour, when it surpassed 10 mass parts, the sheet surface outward appearance was tended to reduce.
Anti-static resin composition of the present invention (A) and olefin resin composition of the present invention (B) suitably can with conventional weather (light) agent, anti-oxidant, heat stabilizer, antiseize paste, silicone oil, plasticizer, lubricant, colouring agent, dyestuff, blowing agent, processing aid (super high molecular weight acrylic acid series polymeric compounds and ultra high molecular weight phenylethylene polymer), fire retardant and the blend of crystal nucleation additive.
In addition, known inorganic or organic filler can with component of the present invention (A) and component (B) blend.Filler in this use for example comprises, glass fibre, glass flake, the milled fibre of glass fibre, glass dust, bead; Hollow Glass Sphere, carbon fiber, the milled fibre of carbon fiber, the for example powder of silver, copper, brass and iron or fibrous material, carbon black, zinc-plated titanium oxide; Zinc-plated silica, nickel-coated carbon fibers, talcum, calcium carbonate, calcium carbonate crystal whisker, wollastonite; Mica, kaolin, imvite, hectolite, ZnOw, potassium titanate crystal whisker; Aluminium borate whisker, piece aluminum oxide, sheet silica and organically-modified terre verte, aramid fibre, phenolic resins and polyester fiber, and they can use or two kinds or the use of more kinds of combination ground individually.
In addition,, can use those that handle with known coupling agent, surface conditioning agent, sizing agent etc., and known coupling agent comprises in order to improve the dispersibility of filler, for example, silane coupler, titanate coupling agent and aluminum coupling agent.
With respect to 100 mass parts component of the present invention (A) and (B) each, above-mentioned inorganic or organic filler is generally used with the 1-200 mass parts.
In addition; Component of the present invention (A) and (B) can be suitably and other known polyblend, for example for example copolymer, ethene and (methyl) acrylic acid copolymer, epoxy resin, phenol resin, carbamide resin and the phenoxy resin of copolymer, polyphenylene oxide, polyphenylene sulfide, aromatic polycarbonate, thermoplastic polyurethane, ethene and (methyl) methyl acrylate of liquid crystal polyester, polyester elastomer, PMMA, methyl methacrylate and maleimide compound of polyamide, polyamide elastomer, polybutylene terephthalate (PBT), PETG, polyarylate, thermoplastic polyester.
Multi-layer sheet of the present invention comprises layer of being made up of said components (A) and the layer of being made up of said components (B) at least.When these two layers were processed sheet material, component (A) and (B) can be in advance through melt kneading all components preparation those maybe can be to make those that sheet material prepares simultaneously through melt kneading all components in extruder.Under latter event, can use those that prepare in advance through the melt kneading all components together.
For melt kneading component in advance, can use various extruders, Banbury mixing machine, kneading machine, continuous kneading machine, roller etc.During mediating, can be with the whole chargings of corresponding component mediating, or the portioning charging is to mediate.
The structure of each of multi-layer sheet of the present invention layer does not receive special restriction, but can be, for example, and foam or hollow.When the layer of being made up of component (B) was foam, blowing agent did not receive special restriction, but for example can be, is used for the known blowing agent of foam polypropylene resin or foamed polyethylene resin.The instantiation of blowing agent comprises inorganic foaming agent for example carbon dioxide, air and nitrogen, but volatile foaming agent for example Celogen Az (ADCA), dinitrosopentamethylene tetramine, azobis isobutyronitrile, hydrazo-dicarbonamide and sodium acid carbonate of aliphatic hydrocarbon, halogenated hydrocarbons and decomposition-type foaming agent for example.They can use or two kinds or the use of more kinds of combination ground individually.In the middle of them, but preferred what use is decomposition-type foaming agent, because can easily regulate molding temperature and foam volume.In addition, the amount to be used of blowing agent does not receive special restriction, but but under the situation of decomposition-type foaming agent, being used for foam moulded resin combination with respect to 100 mass parts, this measures preferably 0.1-10 mass parts.When form by said components (B) the layer be the foaming the time; The component that can suitably use (A) is the anti-static resin composition that comprises 7-30 quality % olefin resin (A-1), 5-20 quality % (being total to) polymer (A-2), 15-50 quality % polymer (A-3) and 20-60 quality % block copolymer (A-4), and condition is that component (A-1), (A-2), (A-3) and summation (A-4) are 100 quality %.
Multi-layer sheet of the present invention can comprise that at least one layer of being made up of the anti-static resin composition of component (A) is with at least one layer of being made up of the olefin resin composition of component (B) and comprise double layer sheet, three-layer tablet material especially and further comprise the multi-layer sheet that has more than above-mentioned layer; The layer that this double layer sheet is made up of component (A) constitutes with the layer that component (B) is formed, the sandwich layer that this three-layer tablet material is made up of component (B) and formed and be laminated to layer formation on this sandwich layer front and back by component (A).Preferably double layer sheet and three-layer tablet material.
The thickness of multi-layer sheet is 0.2-100mm preferably, further preferred 0.5-50mm, especially preferred 0.5-5mm.
In above-mentioned multi-layer sheet, the thickness 10 μ m or higher preferably of the layer of processing by anti-static resin composition of the present invention, further preferred 30 μ m or higher, especially preferred 50 μ m or higher are so that stably show antistatic behaviour.
As the method for the above-mentioned multi-layer sheet of preparation, can use all known methods, their instance comprises following method (1)-(3).
(1) wherein prepares the method (dried laminating method) that the sheet material of sheet material and the component (B) of component (A) bonds together then individually.
(2) wherein in advance component (A) is processed sheet material or film, extrude component (B) then so that extrude-be laminated to the sheet material of component (A) or the method on the film.
(3) wherein with component (A) and (B) method of coextrusion (coextrusion method).
In the middle of them, especially preferred is the coextrusion method.
In above-mentioned, the method that is pre-formed sheet material or film is preferably carried out through T-mould extrusion molding, blow moulding and calendering moulding.In addition, when using the coextrusion method, preferably carry out through multilayer T-mould extrusion molding and multilayer blow moulding, especially preferred multilayer T-mould extrusion molding, and extrude preferably and under 160 ℃-260 ℃, carry out.
Because multi-layer sheet of the present invention is being excellent aspect antistatic behaviour, chemical-resistant, resistance to impact and the appearance, so it can be used as sheet material shape mechanograph.In addition because it is not only excellent but also excellent aspect the vacuum formability at above-mentioned various aspect of performances, so it also can through its vacuum mold is moulded mechanograph for example plate be used for various application.
The mechanograph that so obtains can be used for, and for example, the box field is interconnecting device, wafer case, netting twine box and shielding box for example; Plate for example liquid crystal panel, chip disk, hard disk (HDD), CCD dish, IC dish, organic EL dish, light obtains relevant dish, LED dish and memory disc; Carrier is the IC carrier for example; The protective film that is used for polarization film, light guiding plate and various lens; When cutting off polarization film when the protectiveness sheet material that uses; Sheet material or the film that is used for clean room be dividing plate for example; The internals of automatic vending machine; The antistatic bag that is used for liquid crystal panel, hard disk and plasma panel; The plastics clamp; Be used for the soft box that liquid crystal panel, plasma panel etc. are carried; And other member relevant with the conveying that is used for various parts.
Embodiment
To the present invention be described in more detail via embodiment below.Yet the present invention is in no way limited to these embodiment, only if it breaks away from the scope of the invention really.The ＂ of unit part ＂ among the embodiment and ＂ % ＂ are based on quality, unless otherwise prescribed.In addition, the various measurements among embodiment and the comparative example are based on following method.
1. evaluation method
(1) gel content of rubber-like polymer;
Measure according to said method.
(2) average grain diameter of rubber-like polymer latex;
The average grain diameter that is used to prepare the rubber-like polymer latex of component (A-2) is measured through light scattering method.Use LPA-3100 (by Otsuka Electronics Co., Ltd. makes) to measure according to cumulant method (70 multiplicatrix branch) as measuring machine.The particle size that is dispersed in the graft rubber shaped polymer particle in the component (A-2) adopts almost identical with latex particle electron microscope to confirm.
(3) percent grafting of component (A-2); Measure according to said method.
(4) inherent viscosity (η) of the acetone soluble material of component (A-2);
Measure according to said method.
(5) component (A-3) (the keyed jointing styrene-content of polymer, vinyl bonds content, number-average molecular weight and hydrogenating rate);
(5-1) keyed jointing styrene-content;
The polymer measurement of use before hydrogenation.By the calibration curve that obtains through infrared research based on phenyl at 699cm -1The absorptivity at place is measured.
(5-2) number-average molecular weight;
The polymer measurement of use before hydrogenation.By gel permeation chromatography (GPC).
(5-3) vinyl bonds content;
The polymer measurement of use before hydrogenation.Measure by infrared research (Morello method).
(5-4) hydrogenating rate;
The polymer measurement of use after hydrogenation.By at 100MHz 1The spectrum of unsaturated double-bond reduces calculating, this 100MHz in the H-NMR spectrum 1H-NMR spectrum is measured under 15% concentration of use tetrachloro-ethylene as solvent.
(6) antistatic behaviour;
According to using by United States ETS; Ltd. the FTMS-101 (United States Federal Test Standard) of the STATIC DECAY METER406D that makes; Will+5 under the condition of the moisture of 23 ℃ temperature and 12%RH; 000V is applied on the multi-layer sheet, then this sheet material ground connection is arrived 50V with Measuring Time (second) up to voltage attenuation.
(7) chemical-resistant;
1% strain is applied on the test specimen of multi-layer sheet, and isopropyl alcohol is applied on it.Let this sheet material under 23 ℃, leave standstill then 72 hours.Then, visually estimate the surface condition of sheet material according to following evaluation criterion.
Zero; No change
*; Cracking largely or fragmentation
(8) sheet surface outward appearance;
Visually estimate the surface of multi-layer sheet according to following evaluation criterion.
◎; Surface smoothing, and outward appearance is extraordinary
Zero; Surface smoothing, and outward appearance is good
*; Air spots is sliding, and appearance poor
(9) resistance to impact;
Measure the Dupont impact strength (kgfcm) of multi-layer sheet according to ASTM-D2794.
(10) melt flow rate (MFR) of anti-static resin composition (A);
Melt flow rate (MFR) (g/10min) according to JIS K7210:1999 pellet of the abundant drying of the load measurement component (A) of employing 2.16kg under 230 ℃.
(11) vacuum formability;
With multi-layer sheet vacuum mo(u)lding (preheating under the temperature of heater: 400 ℃) with moulding plate (size: 400mm * 500mm * 50mm).
Zero; Moulding required plate.
*; Moulding is impossible, because sheet material is sagging owing to preheating, or the appearance poor of mechanograph.
2. the component of anti-static resin composition (A)
(1) component (A-1); Acrylic resin
The following acrylic resin that uses Japan Polypropylene Corporation manufacturing is as component of the present invention (A-1).Under 230 ℃ temperature, adopt the load measurement melt flow rate (MFR) of 2.16kg according to JIS K7210:1999.
A1-1; NOVATEC PP FY6C (trade name)
The homopolymerization type, melt flow rate (MFR): 2.4g/10min
A1-2; NOVATEC PP MA3AH (trade name)
The homopolymerization type, melt flow rate (MFR): 10g/10min
A1-3; NOVATEC PP EG6D (trade name)
Random, melt flow rate (MFR): 1.9g/10min
A1-4; NOVATEC PP MG3ATB (trade name)
Random, melt flow rate (MFR): 10g/10min
(2) component (A-2)
(2-1) preparation embodiment 1; ABS resin
Place 75 parts of ion exchange waters, 0.5 part of potassium rodinate, 0.1 part of uncle's lauryl mercaptan, 40 parts of (solid matter) polybutadiene latex (average grain diameters having 7 liters of inner volumes and be equipped with in the glass flask of agitator to flow down at nitrogen; 3,500 dusts, gel content; 85%), 15 parts of styrene and 5 parts of acrylonitrile, and under agitation heat this mixture.When internal temperature reaches 45 ℃, add 0.2 part of sodium pyrophosphate, 0.01 part of ferrous sulfate 7-hydrate and the solution of 0.2 part of glucose in 20 parts of ion exchange waters.Then, add 0.07 part of cumene hydroperoxide with initiated polymerization.After carrying out polymerization one hour; Added 50 parts of ion exchange waters, 0.7 part of potssiumu rodinate, 30 parts of styrene, 10 parts of acrylonitrile, 0.05 part of uncle's lauryl mercaptan and 0.01 part of cumene hydroperoxide continuously 3 hours, the one-step polymerization one hour of going forward side by side.Then, add 0.2 part 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol) to be to stop polymerization.Condense the styrene resin A2-1 that acquisition rubber strengthens with water washing is also dry then with the latex of aqueous sulfuric acid with this product.The percent grafting of this Resin A 2-1 is 68%, and the inherent viscosity of acetone soluble material (η) is 0.45dl/g.
(2-2) preparation embodiment 2; The AS resin
Two are had 30 liters inner volume and are equipped with the polymerization container of the chuck equipment of zonate frond to link together and purge with nitrogen.In first reaction vessel, add 75 parts of styrene, 25 parts of acrylonitrile and 20 parts of toluene continuously.With the solution of 0.12 part of uncle's dodecyl mercaptans and 5 parts of toluene as molecular weight regulator and 0.1 part 1,1 '-solution of azo two (cyclohexane-1-nitrile) and 5 parts of toluene is this first reaction vessel feed continuously as polymerization initiator.In first container, the control polymerization temperature is at 110 ℃, and mean residence time is 2.0 hours, and polymerisation conversion is 57%.Through extracting continuously with the amount identical the polymer solution of gained infeeded second reaction vessel with the quantity delivered of said styrene, acrylonitrile, toluene, molecular weight regulator and polymerization initiator with being provided at the outside pump of first reaction vessel.In second container, polymerization temperature is in 130 ℃, and polymerisation conversion is 75%.To supply with twin-screw 3-graduated discharge extruder so that directly evaporate unreacted monomer and solvent from the copolymer solution that second reaction vessel obtains, to obtain to have the styrene resin A2-2 of inherent viscosity [η] 0.48dl/g.
(2-3) preparation embodiment 3; The styrene resin that rubber strengthens
(2-3-1) preparation of rubber-like polymer (A2-3a)
Drying is equipped with the autoclave of agitator and chuck and purges with nitrogen, and the solution of 20 parts of cyclohexanes and butadiene is placed on wherein.Then, add n-BuLi, and under 50 ℃, carry out the isothermal polymerization.Reach at 100% o'clock at conversion ratio, add 0.75 part of oxolane and 65 parts of butadiene, and heat up from 50 ℃ and to be aggregated to 80 ℃.Reach at 100% o'clock at conversion ratio, to wherein adding 15 parts of styrene, the step of going forward side by side is carried out polymerisation to obtain unhydrided triblock copolymer A-B1-B2.The polymer that is obtained is made up of 15% styrene block (A), 65% butadiene block (B1) and 20% butadiene block (B2); Simultaneously this butadiene block (B1) have 35% 1; 2-contents of ethylene, this butadiene block (B2) have 10% 1, the 2-contents of ethylene; This polymer has 200,000 number-average molecular weight.
In container independently, 1 part of cyclopentadienyl titanium dichloride is dispersed in the cyclohexane, and at room temperature with 0.5 part of triethyl aluminum reaction.The homogeneous solution that is obtained is added in the above-mentioned polymer solution, and under 50 ℃ at 50kgf/cm 2Hydrogen Vapor Pressure under carry out hydrogenation and become basically 100% up to hydrogenating rate, to obtain rubber-like polymer A2-3a.
(2-3-2) preparation of the styrene resin (A2-3) of rubber enhancing
Purge the autoclave that is equipped with zonate frond and processes by stainless steel with nitrogen; Flow down to wherein adding 28 parts of (solid matter) above-mentioned polymer A 2-3a, 10.8 parts of styrene, 7.2 parts of acrylonitrile, 54 parts of methyl methacrylates, 120 parts of toluene and 0.1 part of uncle's dodecyl mercaptans as the homogeneous solution for preparing in advance in the toluene of solvent at nitrogen then, and under agitation heat this mixture.When internal temperature reaches 50 ℃, to wherein adding 0.5 part of benzoyl peroxide and 0.1 part of dicumyl peroxide, and further improve temperature.Reach after 80 ℃ in temperature, control temperature constant at 80 ℃ to carry out polymerization.After initiated polymerization six hours, in one hour, temperature is brought up to 120 ℃, and then carried out polymerization two hours, then cessation reaction.Conversion ratio is 97%.
Be cooled to after 100 ℃ at reactant mixture, to wherein adding 0.2 part 2,2-di-2-ethylhexylphosphine oxide-4-6-tert-butyl phenol.Then, from this autoclave, discharge reactant mixture, distill out unreacted matters and solvent through steam distillation then.In degassing extruder, the resulting polymers granulation is obtained polymer A 2-3.Its percent grafting is 45%, and the inherent viscosity of acetone soluble material [η] is 0.45dl/g.
(2-4) preparation embodiment 4; The styrene resin that rubber strengthens
With with prepare embodiment 3 in the same method carry out polymerisation; Difference is to use 19 parts of ethylene-propylene rubber (＂ EP84 ＂ (trade name); Make by JSR Corporation) replace rubber-like polymer A2-3a and use 57 parts of styrene and 24 parts of acrylonitrile to replace styrene/acrylonitrile/methyl methacrylate; And obtaining polymer A 2-4, it has 20% ethylene-propylene rubber content, the inherent viscosity [η] of the acetone soluble material of 55% percent grafting and 0.45dl/g.
(3) component (A-3)
(3-1) preparation embodiment 5; Partially hydrogenated SBS
Drying is equipped with the autoclave of agitator and chuck and purges with nitrogen, and will contain 30 cinnamic cyclohexane solutions and be placed on wherein.Then, add n-BuLi, and under 70 ℃, carry out after the polymerization 1 hour, add contain 40 parts of butadiene cyclohexane solution to carry out polymerization 1 hour.In addition, interpolation contains 30 parts of cinnamic cyclohexane solutions to carry out polymerization 1 hour.The block polymer solution that a sampling part is obtained, and with respect to 0.3 part 2 of 100 parts of block copolymers interpolation, 6-two-tert-butyl catechol removes through heating then and desolvates.This material have 60% styrene-content and in the polybutadiene part 35% 1,2-contents of ethylene, and have 74,000 number-average molecular weight.With adding in the remaining block copolymer solution through the solution that cyclopentadienyl titanium dichloride and triethyl aluminum is reacted obtain in cyclohexane, and under 50 ℃ at 50kgf/cm 2Hydrogen Vapor Pressure under carried out hydrogenation 40 minutes.Add 0.3 part 2 with respect to 100 parts of block copolymers, 6-two-tert-butyl catechol obtains polymer A 3-1 then except that desolvating, and wherein the hydrogenating rate of butadiene part is 69%.
(3-2) preparation embodiment 6; The SBS of complete hydrogenation
Drying is equipped with agitator and chuck mesohigh still and purges with nitrogen, and the solution of 20 parts of butadiene in cyclohexane is placed on wherein.Then, add 0.025 part of n-BuLi, and under 50 ℃, carry out the isothermal polymerization.Reach at 100% o'clock at conversion ratio, to wherein adding 0.75 part of oxolane and 65 parts of butadiene, and heat up from 50 ℃ and to be aggregated to 80 ℃.Reach at 100% o'clock at conversion ratio, to wherein adding 15 parts of styrene, the step of going forward side by side is carried out polymerisation to obtain unhydrided triblock copolymer A-B1-B2.As with prepare embodiment 5 in the same method carry out the result of sampling and analysing; The polymer that is obtained is by 15% styrene block (A block), 1; The 2-contents of ethylene is 35% butadiene block (B-1 block) and 1; The 2-contents of ethylene is 10% butadiene block (B2 block) composition, and has 200,000 number-average molecular weight.
In container independently, 1 part of cyclopentadienyl titanium dichloride is dispersed in the cyclohexane, and at room temperature with 0.5 part of triethyl aluminum reaction.The homogeneous solution that is obtained is added in the above-mentioned polymer solution, and under 50 ℃ at 50kgf/cm 2Hydrogen Vapor Pressure under carried out hydrogenation 2 hours.With preparation embodiment 5 similarly, add 2,6-two-tert-butyl catechol removes then and desolvates and obtain hydrogenating rate and be essentially 100% hydropolymer (A3-2).
(3-3) preparation embodiment 7; SBS
Drying is equipped with the chuck autoclave of agitator and purges with nitrogen.Flow down at nitrogen, to wherein adding cyclohexane and 0.08 part of oxolane.Improve temperature then, and when internal temperature reaches 70 ℃, add the cyclohexane solution that contains 0.052 part of n-BuLi.Replenish 15.5 parts of styrene, 60 minutes (phase I) of this mixture of polymerization then for the gained mixture then.Next, add by 3 parts of styrene and 20 parts of mixtures that butadiene constitutes, and the mixture of polymerization gained 60 minutes (second stage).Add once more by 3 parts of styrene and 20 parts of mixtures that butadiene constitutes, and 60 minutes (phase III) of the mixture of polymerization gained.Add once more by 3 parts of styrene and 20 parts of mixtures that butadiene constitutes, and the mixture of polymerization gained 60 minutes (stage), to allow three tapered polymerizations.Next, add 15.5 parts of styrene, and the mixture of polymerization gained 60 minutes (five-stage).Polymerisation conversion is 100%.
Between polymerization period, the control internal temperature is at 70 ℃.After polymerization was accomplished, with 2,6-two-tert-butyl catechol replenished this polymer solution; Being similar to preparation embodiment 5 then desolvates through heating to remove; And obtain block copolymer A3-3, and it has 3 tapered, and this block has the polystyrene that in polybutadiene block, increases gradually.This copolymer has 128,000 number-average molecular weight and 40% styrene-content.
(3-4) preparation embodiment 8; Styrene-butadiene is the teleblock copolymer radially
Drying is equipped with the chuck autoclave of agitator and purges with nitrogen.Flow down at nitrogen, to wherein adding cyclohexane and 2.75 parts of oxolanes.Replenish this mixture with 25 parts of styrene, and with temperature increase to 60 ℃.Replenish this mixture, 60 minutes (phase I) of polymerization gained mixture then with the cyclohexane solution that contains 0.175 part of n-BuLi then.Next, add by 3 parts of styrene and 20 parts of mixtures that butadiene constitutes, and the mixture of polymerization gained 60 minutes (second stage).Next, add by 3 parts of styrene and 20 parts of mixtures that butadiene constitutes, and 60 minutes (phase III) of the mixture of polymerization gained.Next, add 29 parts of butadiene, and carry out polymerization up to reaching 100% conversion ratio.Replenish the mixture of gained with 0.1 part of silicon tetrachloride as coupling agent, and accomplish coupling reaction.After polymerization was accomplished, with 2,6-two-tert-butyl catechol replenished this polymer solution, and be similar to preparation embodiment 5 then and desolvate through heating to remove, and the coupling type styrene-butadiene block copolymer A3-4 that acquisition has tapered.This copolymer has 31% styrene-content and 200,000 number-average molecular weight.
(4) component (A-4)
Use is by Sanyo Chemical Industries, and the following polymer that Ltd. makes is as component of the present invention (A-4).
A4-1; PELESTAT 230 (trade names; Polyolefin-polyether block copolymer)
A4-2; PELESTAT303 (trade name; Polypropylene-polyether block copolymer)
(5) other component
Following material is used as other component so that improve antistatic behaviour.
D1; Non-ionic antistatic agent ELECTROSTRIPPER TS-5 (trade name; Glyceride by the KaoCorporation preparation)
D2; Trifluoromethayl sulfonic acid lithium SANKONOL AQ-75T (trade name; By SankoChemical Co., 75% aqueous solution of the trifluoromethayl sulfonic acid lithium of Ltd. preparation)
D3; ZnOw PANATETRA WZ-0501 (trade name; By MatsushitaElectric Industrial Co., the Ltd. preparation)
(5) use following polypropylene by Japan Polypropylene Corporation preparation as component (B-1).
Under 230 ℃ temperature, adopt the load measurement melt flow rate (MFR) of 2.16kg according to JIS K7210:1999.
B1-1; NOVATEC PP EA9BT (trade name)
The homopolymerization type, melt flow rate (MFR): 0.5g/10min
B1-2; NOVATEC PP EG8 (trade name)
Random, melt flow rate (MFR): 0.8g/10min
(6) use the following polyethylene for preparing by Japan Polyethylene Corporation as component (B-2).
Under 190 ℃ temperature, adopt the load measurement melt flow rate (MFR) of 2.16kg according to JIS K6922-2.
B2-1; NOVATEC LD LF122 (trade name)
Low density polyethylene (LDPE), melt flow rate (MFR): 0.3g/10min
B2-2; NOVATEC LD LF280H (trade name)
Low density polyethylene (LDPE), melt flow rate (MFR): 0.7g/10min
B2-3; NOVATEC LD LF440HB (trade name)
Low density polyethylene (LDPE), melt flow rate (MFR): 2.8g/10min
Embodiment 1-24, comparative example 1-10
In the Henschel mixer, with the blending ratio of table shown in the 1-2 component of component (A) is mixed, then this mixture of melt kneading and obtain pellet in double screw extruder (cylinder temperature is set to 220 ℃) by table 1-1.The dry fully pellet that is obtained is measured the melt flow rate (MFR) of this pellet then in a manner described.The result is shown in Table 2.
In embodiment 1-20 and comparative example 1-10; Use three-layer tablet material extrusion equipment to obtain the three-layer tablet material by table 1-1 with said components (A) and the component (B) shown in the table 1-2, this sheet material is made up of the intermediate layer of component (B) and two superficial layers (on the front and back in this intermediate layer) of component (A).Extruder through being arranged in 190 ℃-240 ℃ the temperature range prepares the three-layer tablet material.
This three-layer tablet material has the thickness of 1mm, and wherein the intermediate layer has the thickness of 0.8mm, and two superficial layers have the thickness of 0.1mm separately.In addition, and (B-2) and add the extruder of three layers of extrusion equipment by the component (B-1) in the blending ratio mixing intermediate layer shown in the table 1.
Antistatic behaviour, chemical-resistant, resistance to impact and the sheet surface outward appearance of the three-layer tablet material that is obtained through above-mentioned evaluation method evaluation, the result is shown in Table 2.
In addition, use above-mentioned three-layer tablet material to carry out vacuum mo(u)lding (heter temperature: 400 ℃, preheating time: 20-45 second).Evaluation result is shown in Table 2.
In embodiment 21-24, through multilayer T-mould extrusion equipment under 190 ℃ by said components (A) and component (B) the moulding three-layer tablet material of table shown in the 1-1, simultaneously with azodicarbonamide foaming agent further with component (B) blend.The three-layer tablet material of preparation has the gross thickness of 3mm, and wherein the intermediate layer has 2 foaming magnifying power, and two superficial layers have the thickness of 30 μ m separately.
Antistatic behaviour, chemical-resistant and the sheet surface outward appearance of the three-layer tablet material that is obtained through above-mentioned evaluation method evaluation, the result is shown in Table 2.
Figure G2007800102766D00371
Figure G2007800102766D00381
[table 2]
Figure G2007800102766D00391
Draw following from the result shown in the table 2.
The multi-layer sheet of embodiment of the invention 1-20 is being excellent aspect antistatic behaviour, chemical-resistant, resistance to impact, appearance and the vacuum formability.The multi-layer sheet of embodiment of the invention 21-23 is being excellent aspect antistatic behaviour, chemical-resistant and the appearance.
The comparative example 1, and the blending amount of treating of the olefin resin (A-1) of anti-static resin composition wherein of the present invention (A) is lower than the scope of the invention, is wanting in antistatic behaviour, chemical-resistant, resistance to impact, sheet surface outward appearance and vacuum formability.The comparative example 2, wherein component (A-1) treat that blending amount surpasses the scope of the invention and component (A-2), (A-3) and the blending amount of treating (A-4) are lower than the scope of the invention, be wanting in antistatic behaviour and resistance to impact.The comparative example 3, and the blending amount of treating of the component (A-4) of anti-static resin composition wherein of the present invention (A) is lower than the scope of the invention, is wanting in antistatic behaviour.The comparative example 4, and wherein the blending amount of treating of component (A-4) surpasses the scope of the invention, are wanting in resistance to impact and sheet surface outward appearance.The comparative example 5, and the blending amount of treating of the component (A-3) of anti-static resin composition wherein of the present invention (A) is lower than the scope of the invention, is wanting in resistance to impact.The comparative example 6, and wherein the blending amount of treating of component (A-3) surpasses the scope of the invention, are wanting in resistance to impact and sheet surface outward appearance.The comparative example 7, and wherein the melt flow rate (MFR) of the component (B-1) of olefin resin composition (B) is higher than the scope of the invention, is wanting in vacuum formability.The comparative example 8, and wherein the melt flow rate (MFR) of component (B-2) is higher than the scope of the invention, is wanting in vacuum formability.Handle the comparative example 9 of the blending ratio in the olefin resin composition of the present invention (B), wherein the amount to be used of component (B-1) is lower than the scope of the invention above the amount to be used of the scope of the invention and component (B-2), is wanting in vacuum formability.The comparative example 10, and wherein the amount to be used of component (B-1) amount to be used that is lower than the scope of the invention and component (B-2) surpasses the scope of the invention, is wanting in sheet surface outward appearance and vacuum formability.
Industrial applicability
Multi-layer sheet of the present invention is compared aspect antistatic behaviour, chemical-resistant, resistance to impact, appearance and vacuum formability excellent with conventional multi-layer sheet, so it can be suitable for wherein requiring the for example various parts in vehicular field, electric/electronic field, office automation (OA) and household appliance technical field and the health field of high performance field.

Claims (6)

1. multi-layer sheet, it comprises layer of being made up of following component (A) and the foaming layer of being made up of following component (B) at least:
Component (A):
The anti-static resin composition that comprises following component:
The component (A-1) of 7-30 quality %: olefin resin;
The component (A-2) of 5-20 quality %: the styrene resin that strengthens through the rubber that the polymerization of vinyl monomer that comprises aromatic vinyl compound is obtained, and/or the polymer that under the situation of this rubber-like polymer not, the said polymerization of vinyl monomer that comprises aromatic vinyl compound is obtained;
The component (A-3) of 15-50 quality %: at least a being selected from comprises mainly the polymer blocks is made up of aromatic vinyl compound and the block copolymer of the main polymer blocks of being made up of conjugated diene compound and the polymer of its hydrogenated products; With
The component (A-4) of 20-60 quality %: comprise the block copolymer of olefin polymer block and hydrophilic polymer block, condition be said components (A-1), (A-2), (A-3) and summation (A-4) be 100 quality % and
Component (B):
The olefin resin composition that comprises following component:
The component (B-1) of 60-97 quality %: under 230 ℃ temperature, adopt the melt flow rate (MFR) of the load measurement of 2.16kg to be no more than the acrylic resin of 2.0g/10min according to JIS K7210:1999; With
The component (B-2) of 3-40 quality %: under 190 ℃ temperature, adopt the melt flow rate (MFR) of the load measurement of 2.16kg to be no more than the polyvinyl resin of 2.0g/10min according to JIS K6922-2.
2. according to the multi-layer sheet of claim 1, wherein this component (A) has the melt flow rate (MFR) of 1.0-15g/10min, and it adopts the load of 2.16kg to measure under 230 ℃ temperature according to JIS K7210:1999.
3. according to the multi-layer sheet of claim 1 or 2, wherein this olefin resin (A-1) is the random copolymer of propylene and ethene.
4. according to the multi-layer sheet of claim 1, it is the three-layer tablet material, and this three-layer tablet material is formed and the layer that is laminated on this sandwich layer front and back constitutes by sandwich layer with by component (A), and this sandwich layer is made up of component (B).
5. according to the multi-layer sheet of claim 1, wherein it obtains through the coextrusion method.
6. mechanograph, it is by according to each multi-layer sheet vacuum mo(u)lding among the claim 1-5.
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TW200604281A (en) * 2004-06-25 2006-02-01 Techno Polymer Co Ltd Thermoplastic resin composition and molded article

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