CN101875824A - Anti-static resin composition, antistatic/pressure-sensitive-adhesive resin composition, pressure-sensitive adhesive film and their preparation method - Google Patents
Anti-static resin composition, antistatic/pressure-sensitive-adhesive resin composition, pressure-sensitive adhesive film and their preparation method Download PDFInfo
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
- C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
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- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
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- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
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- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
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Abstract
The invention provides formed material, it is good anti-static function and moulded product in appearance, preferably also is good on transparency and thermotolerance, can be used as the bonding coat of pressure-sensitive adhesive film and the formed material of supporter.The anti-static resin composition that provides comprises: (A) polyolefin resin; (B) comprise the segmented copolymer of olefin polymer block and hydrophilic polymer block; (C) at least a polymkeric substance that contains unitary polymkeric substance of conjugated diene compound and hydrogenated products thereof that is selected from.Can control binding property by the combined amount of regulating composition (A).When composition (A) comprise contain cycloalkene unit have 60 to 200 ℃ of polyolefin resines of second-order transition temperature the time, thermotolerance improves.The preferred example of composition (C) is segmented copolymer and hydrogenated products thereof, and described segmented copolymer comprises conjugated diene compound polymer blocks and polymerization of aromatic vinyl thing block.
Description
The application is that application number is that PCT/JP20061306254, the applying date to be on 03 28th, 2006, denomination of invention enter dividing an application of China national phase application for the international application of " anti-static resin composition, antistatic/pressure-sensitive-adhesive resin composition, pressure-sensitive adhesive film and their preparation method ".
Technical field
The present invention relates to give moulded product for example film and sheet material excellent antistatic matter anti-static resin composition, be suitable for moulded product for example form on film and the sheet material high resistance static bonding coat antistatic/pressure-sensitive-adhesive resin composition, have the pressure-sensitive adhesive film of the antistatic bonding coat that comprises antistatic/pressure-sensitive-adhesive resin composition, and their preparation methods.More specifically, the present invention relates to anti-static resin composition, it has excellent antistatic matter and transparency, when forming moulded product good appearance is for example also arranged during film, and relating to antistatic/pressure-sensitive-adhesive resin composition, it is good on anti-static function and viscosity, and bond strength is controlled easily, and relating to by using moulded product that these compositions prepare for example pressure-sensitive adhesive film, sheet material and laminating material, and the preparation method who relates to them.
Background technology
The pressure-sensitive adhesive film of bonding coat is set on supporter, is widely used in office automation (OA) and household appliance technical field, in building material field; in the field that relates to liquid crystal; in the field of mobile telephone, for example, as various objects for example the surface protection film of spacer and window glass use.Pressure-sensitive adhesive film simultaneously is provided with bonding coat and at the supporter another side peel ply is set at supporter usually, direct coiled roller, perhaps interleaving paper etc. be attached at the bonding coat hub disk around, described bonding coat forms in the one side of supporter.Under the situation in front, peel off pressure-sensitive adhesive film from peel ply, bonding coat pastes mutually with the object that will cover then.Under the situation of back, when using, peel off interleaving paper, bonding coat pastes mutually with the object that will cover then.When pressure-sensitive adhesive film is used to protect the object surfaces that will cover, before being applied to the object that will cover, pressure-sensitive adhesive film is peeled off.In this case, produce static (hereinafter being referred to as to peel off to electrify), this causes peeling off film such as processing, that is, and and the problem that workability worsens, and, because the film that attracts dust to peel off is dirty easily.In these problems some are attributable to bonding coat, other be attributable to supporter, the both needs to solve.
For the problems referred to above, peel off the film that electrifies particularly for the surface of protection liquid crystal display polarising sheet and produce significant problem.Along with the liquid crystal display screen becomes bigger, it is higher that resolving power becomes, and it is thinner that framework becomes, and it is littler that thickness becomes, and it is narrower that the IC circuit becomes on live width, poorer to the electrostatic tolerance.Therefore, peel off to electrify and become the reason that product production descends.
As solution to the problems described above, at patent documentation 1 pressure-sensitive adhesive tape has been proposed, wherein the one side at the supporter that is made of polyethylene terephthalate (PET) film forms peel ply, Jie forms bonding coat by antistatic layer at another side, but existing problems, for example to peel off the effect that electrifies not enough and owing to supporter produces static in prevention.In patent documentation 2, disclose pressure-sensitive adhesive film, electrified, existed for example owing to supporter produces the such problem of static although eliminated peeling off of taking place on the bonding coat to a certain extent with the bonding coat that contains charge control agent.
And, surface protection film is disclosed in patent documentation 3, it uses polyolefin film as support film, and the segmented copolymer that is made of styrene polymer block and conjugated diolefin polymer block is used as pressure sensitive adhesive.Equally, disclose surface protection film in patent documentation 4, wherein polyolefin film is used as support film, and the above-mentioned segmented copolymer with partially hydrogenated conjugated diolefin polymer is used as pressure sensitive adhesive.But these surface protection films can not satisfy the requirement that electrifies of peeling off to preventing from as above to mention recently.
In addition; surface protection film is disclosed in patent documentation 5; it is by being laminated to bonding coat on the antistatic layer; described antistatic layer is in turn laminated to the one or both sides of the sheet substrate that the film by for example polyolefin resin constitutes, and further pressure-sensitive adhesive layer is laminated on the bonding coat of as above mentioning to form.But, this film existing problems, as when antistatic layer forms with an organic solvent owing to require the measure of prevention environmental pollution, therefore make process become complexity with unfavorable economically.This film has another problem, even antistatic layer forms as the middle layer, antistatic property is not enough, particularly on the sheet supporter.
Patent documentation 1: Japanese kokai publication hei 8-134416
Patent documentation 2: TOHKEMY 2004-155977
Patent documentation 3: Japanese kokai publication sho 54-126243
Patent documentation 4: Japanese kokai publication sho 61-103975
Patent documentation 5: TOHKEMY 2000-328024
Summary of the invention
As above describe in detail, need improve anti-static function the supporter both of bonding coat and pressure-sensitive adhesive film.
In addition, depend on the use of pressure-sensitive adhesive film or sheet material, require for example transparency and stable on heating feature sometimes.For thermotolerance, for example, when pressure-sensitive adhesive film was printed on the face of supporter, it must be resisted and surpass 80 ℃ temperature when the printing after drying, under the situation of anti-static sheet, required at high temperature not take place for example to twist and such distortion of curling.In addition, must to have be acceptable outward appearance in practice at least for two kinds of moulded products.
The purpose of this invention is to provide anti-static resin composition, it is good on anti-static function and transparency, also is good on appearance during film for example when forming moulded product.
Another object of the present invention provides antistatic/pressure-sensitive-adhesive resin composition, and it is good on anti-static function and viscosity, controls bond strength and the formation that is suitable for bonding coat easily.
The present invention also has another purpose to provide pressure-sensitive adhesive film and preparation method thereof, described pressure-sensitive adhesive film is good on anti-static function, a supporter and antistatic bonding coat are arranged, both are enough combinations doughtily mutually, bonding coat comprises above-mentioned antistatic/pressure-sensitive-adhesive resin composition, and good pressure-sensitive adhesive film of transparency and preparation method thereof preferably is provided.
The present invention even also have another purpose to provide anti-static resin composition, it can provide various anlistatig moulded product for example film and sheet material and antistatic lamination material, maybe can be provided for the supporter of above-mentioned pressure-sensitive adhesive film, it is good thermotolerance and moulded product in appearance.
To achieve these goals, the inventor has implemented intensive research, found that the composition that comprises polyolefin resin, specific segmented copolymer and specific conjugated diolefin polymer with specified quantitative is good on anti-static function and transparency.In addition, discovery also is good on binding property with the composition that specified quantitative comprises these compositions, particularly can easily control its bond strength by type and the add-on of selecting polyolefin resin.And, discovery is good aspect bonding between supporter and bonding coat and aspect the transparency also is being good antistatic/pressure-sensitive adhesive film, can obtain by the bonding coat that forms above-mentioned binder composition on the surface of appropriate resin composition supporter.
And, to achieve these goals, the inventor has implemented intensive research, found that not only keep excellent antistatic matter and also on thermotolerance also be good resin combination can by use with certain ratio contain the cycloolefin composition for example the polyolefin resin of norbornylene obtain as the said polyolefins resin.And, find that the good moulded product of anti-static function can when being shaped to sheet material or film and being laminated on other resin formed article, can also provide anti-static function good laminating material by this resin combination moulding is obtained.
Therefore, provide anti-static resin composition, it is characterized in that comprising according to one aspect of the invention:
(A) polyolefin resin of 30 to 95 quality % (except the following ingredients (B))
(B) segmented copolymer that comprises olefin polymer block and hydrophilic polymer block of 5 to 20 quality %; With
(C) at least a polymkeric substance (condition is that mentioned component (A), (B) and summation (C) are 100 quality %) that contains unitary polymkeric substance of conjugated diene compound and hydrogenated products thereof that is selected from of 0 to 50 quality %.
Anti-static resin composition of the present invention can provide for example film of moulded product, and it is not only on anti-static function but also in transparency with also be good in appearance.
According to another aspect of the present invention, provide antistatic/pressure-sensitive-adhesive resin composition, it is characterized in that comprising:
(A) polyolefin resin of 0 to 59 quality % (except the following ingredients (B)),
(B) segmented copolymer that comprises olefin polymer block and hydrophilic polymer block of 3 to 60 quality %; With
(C) at least a polymkeric substance (condition is that mentioned component (A), (B) and summation (C) are 100 quality %) that contains unitary polymkeric substance of conjugated diene compound and hydrogenated products thereof that is selected from of 35 to 97 quality %.
Antistatic/pressure-sensitive-adhesive resin composition of the present invention can provide for example film of moulded product, it also is suitable for forming transparent adhesive layer on the supporter that is formed by polymer composition not only on anti-static function but also in transparency with also be good in appearance.
According to first preferred embodiment of antistatic/pressure-sensitive-adhesive resin composition of the present invention, provide the antistatic/pressure-sensitive-adhesive resin composition (condition is that mentioned component (A), (B) and summation (C) are 100 quality %) of the mentioned component (C) of the mentioned component (B) of the mentioned component (A) that comprises 0 to 40 quality %, 6 to 25 quality % and 35 to 94 quality %.
Antistatic/pressure-sensitive-adhesive resin composition according to first preferred embodiment can be suitable for forming transparent bonding coat to obtain transparent film on the support film that is made of polyolefin resin.
Second preferred embodiment according to antistatic/pressure-sensitive-adhesive resin composition of the present invention, antistatic/pressure-sensitive-adhesive resin composition is provided, it comprises the mentioned component (A) of 0 to 59 quality %, the mentioned component (C) of the mentioned component of 3 to 60 quality % (B) and 40 to 97 quality %, wherein mentioned component (A) is by polyolefine of functional group modification (A '-1) and/or polyolefine (A '-2), mentioned component (C) is the hydrogenated products of the polymkeric substance that mainly is made of conjugated diene compound unit and aromatic ethenyl compound unit, in this case, preferred mentioned component (C) is hydrogenated.
Antistatic/pressure-sensitive-adhesive resin composition according to second preferred embodiment is suitable for forming transparent bonding coat to obtain transparent film on by the different polymer compositions support film that for example styrene resin constitutes.
Therefore, can use anti-static resin composition of the present invention and antistatic/pressure-sensitive-adhesive resin composition of the present invention and obtain various laminating materials.
As the preferred laminating material of the present invention, can illustration following (1) to (4):
(1) pressure-sensitive adhesive film, be characterised in that and comprise the supporter that constitutes by polyolefine resin composition, and be arranged on described supporter at least the one side on antistatic bonding coat, described antistatic bonding coat is made of antistatic/pressure-sensitive-adhesive resin composition of the present invention, is preferably the antistatic/pressure-sensitive-adhesive resin composition according to above-mentioned first embodiment.
(2) according to the pressure-sensitive adhesive film of above-mentioned (1) item, wherein the said polyolefins resin combination is an anti-static resin composition of the present invention.
(3) pressure-sensitive adhesive film, be characterised in that and comprise the supporter that constitutes by thermoplastic polymer composition, and be arranged on described supporter at least the one side on antistatic bonding coat, described antistatic bonding coat is made of antistatic/pressure-sensitive-adhesive resin composition of the present invention, preferably according to the antistatic/pressure-sensitive-adhesive resin composition of above-mentioned second embodiment.
(4) with the laminating material of adhesive sheet or form membrane, be characterised in that and comprise the supporter that constitutes by thermoplastic polymer composition, and be arranged on antistatic/pressure-sensitive adhesive layer on the one side at least of described supporter, described antistatic/pressure-sensitive adhesive layer is made of the antistatic/pressure-sensitive-adhesive resin composition of above-mentioned first or second embodiment according to the present invention.
The sheet material of above-mentioned (1) to (4) or film can be by preparation method's preparations of pressure-sensitive adhesive sheets or film, and described method is characterised in that the step that comprises the coextrusion resin combination is to form supporter and antistatic/pressure-sensitive-adhesive resin composition of the present invention.
When mentioned component (A) comprises polyolefin resin (A-1) and polyolefin resin (A-2), and when ((A-1)/(A-2)) both content ratios are 95/5 to 1/99 (quality ratio) in anti-static resin composition of the present invention and the antistatic/pressure-sensitive-adhesive resin composition, thermotolerance improves, wherein polyolefin resin (A-1) contains cycloalkene unit and has 60 to 200 ℃ of second-order transition temperatures, and polyolefin resin (A-2) does not contain cycloalkene unit.
In this anti-static resin composition and antistatic/pressure-sensitive-adhesive resin composition, preferred mentioned component (C) is at least a polymkeric substance that is selected from segmented copolymer and hydrogenated products polymkeric substance thereof, and described segmented copolymer contains polymer blocks (c1) and the main polymer blocks (c2) that is made of the aromatic ethenyl compound unit that mainly is made of the conjugated diene compound unit.
In order to improve anti-static function, anti-static resin composition of the present invention and antistatic/pressure-sensitive-adhesive resin composition preferably further contain at least a anti-static function activator (E) of composition (E1), composition (E2), composition (E3) and composition (E4) in greater detail that is selected from hereinafter, its consumption is enough to improve the anti-static function of above-mentioned anti-static resin composition, accounts for 0.01 to 30 part in per 100 parts of mentioned component (A), (B) and the summation (C) in mass usually.
Because anti-static resin composition of the present invention contains special component (A), (B) and (C) with predetermined amount separately, is good on anti-static function and transparency, and when it be made into moulded product for example during film its appearance be good.Particularly when composition (A) by the above-mentioned polyolefin resin of mentioning (A-1) and (A-2) constitutes, can obtain to have stable on heating moulded product.
Because antistatic/pressure-sensitive-adhesive resin composition of the present invention contains specific composition (A), (B) and (C) with predetermined amount separately, its anti-static function, transparency and viscosity are good, and control bond strength easily.
Antistatic/pressure-sensitive-adhesive resin composition of the present invention provides at the antistatic bonding coat good to the viscosity of supporter.Particularly when support film was made of anti-static resin composition of the present invention, it was good that film is made as a whole anti-static function, obtained to be no more than 10 under predetermined condition
9The surface resistivity of Ω.
When support film is made of anti-static resin composition of the present invention, can obtain anti-static function and transparency, outward appearance, the bonding good pressure-sensitive adhesive film between supporter and antistatic bonding coat.
The preparation method of pressure-sensitive adhesive film according to the present invention can easily be formed on the bonding good pressure-sensitive adhesive film between supporter and the antistatic bonding coat.
Description of drawings
Fig. 1 is the summary sectional view of an example of expression pressure-sensitive adhesive film of the present invention;
Fig. 2 is illustrated in the summary sectional view of an example that antistatic bonding coat surface is provided with the pressure-sensitive adhesive film of protective layer;
Fig. 3 is the summary sectional view of an example of each surface of being illustrated in supporter pressure-sensitive adhesive film of being provided with antistatic bonding coat and protective layer; With
Fig. 4 is the summary sectional view of an example of three layers of thin slice of the anti-static resin composition formation of expression the application of the invention.
Nomenclature
1,1 ' and 1 " pressure-sensitive adhesive film
11 supporters
12, the antistatic bonding coat of 12a and 12b
13,13a and 13b protective layer
2 three-layer tablet materials
The layer that 21a and 21b form with anti-static resin composition of the present invention
22 middle layers
Embodiment
Hereinafter, the present invention is described in detail.In this specification sheets, term " (being total to) polymkeric substance " means homopolymer and multipolymer, and term " (methyl) acryl " means acryl and/or methacryloyl, and term " (methyl) acrylate " means acrylate and/or methacrylic ester.
1. anti-static resin composition
Anti-static resin composition of the present invention is characterised in that and comprises:
(A) polyolefin resin of 30 to 95 quality % (be also referred to as " composition (A) " in the present invention, it gets rid of following ingredients (B)),
(B) 5 to 20 quality % comprise the segmented copolymer (being also referred to as " composition (B) " in the present invention) of olefin polymer block and hydrophilic polymer block; With
(C) at least a polymkeric substance (being also referred to as " composition (C) " in the present invention) (condition is that mentioned component (A), (B) and summation (C) are 100 quality %) that contains unitary polymkeric substance of conjugated diene compound and hydrogenated products thereof that is selected from of 0 to 50 quality %.
1-1. composition (A)
Mentioned component (A) is a polyolefin resin, and it comprises the alkene that is no less than 2 carbon atoms as constituting monomeric unit, as long as it does not become just not restriction especially of composition described below (B).In the present invention, preferred component (A) is for containing alkene with 2 to 10 carbon atoms as (being total to) polymkeric substance that constitutes monomeric unit.
The preferred embodiment of composition of the present invention (A) comprising:
(1) (is total to) polymkeric substance, wherein constitutes monomeric unit and mainly at least aly constitute (hereinafter being referred to as " polymkeric substance (1) ") by what be selected from the alkene that is no less than two carbon atoms; With
(2) (be total to) polymkeric substance, wherein constitute monomeric unit and mainly have at least a of the alkene that is no less than two carbon atoms and be selected from and to constitute (hereinafter being referred to as " polymkeric substance (2) ") with the compound of described olefin-copolymerization at least a by being selected from.
These polymkeric substance can use separately or two or more are used in combination.
As polyolefin resin mentioned above, can use any in those polymkeric substance that obtain with these known polymerization methods of for example high pressure polymerization process, low-pressure polymerization method and metallocenes catalysis process.
As above-mentioned alkene, typically use the non-cyclic olefin class, its concrete example comprises ethene and alpha-olefin for example propylene, 1-butylene, 1-amylene, 1-hexene, 3-methyl-1-butene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 3-ethyl-1-amylene, 4-methyl isophthalic acid-hexene, 4,4-dimethyl-1-amylene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid and 1-eicosylene.These alkene can use separately or two or more are used in combination.In these alkene, optimal ethylene, propylene, 1-butylene, 3-methyl-1-butene and 4-methyl-1-pentene, special optimal ethylene and propylene.
As above-mentioned alkene, can also use the cyclenes hydro carbons.Cycloolefin uses with the non-cyclic olefin of as above mentioning usually.
Cycloolefin is restriction especially not, as long as it contains a two key, for example is included in the compound of example explanation among the Japanese kokai publication hei 5-310845.Preferred cycloolefin is to have 11 or the compound of carbon atom still less.
As above-mentioned cycloolefin, the norbornylene class is preferred.Preferably have 11 or still less the norbornylene class of carbon atom (norbornylene and/or norbornene derivative) account for the 50 quality % that are not less than of whole cyclenes hydro carbons.The specific examples of norbornylene class comprises 2-norbornylene (two ring [2.2.1] hept-2-ene"s), 6-methyl bicyclic [2.2.1] hept-2-ene", 6-ethyl two ring [2.2.1] hept-2-ene"s, 6-normal-butyl two ring [2.2.1] hept-2-ene"s, 6-isobutyl-two ring [2.2.1] hept-2-ene"s, 5,6-dimethyl two ring [2.2.1] hept-2-ene"s, 1-methyl bicyclic [2.2.1] hept-2-ene", 7-methyl bicyclic [2.2.1] hept-2-ene", three ring [4.3.0.1
2.5]-3-decene, 2-methyl three ring [4.3.0.1
2.5]-3-decene, 5-methyl three ring [4.3.0.1
2.5]-3-decene, three ring [4.4.0.1
2.5]-3-undecylene etc.These cycloolefins can use separately or two or more are used in combination.
In addition, the cycloolefin with 12 or more carbon atoms can use separately or with as above mention have 11 or still less the compound of carbon atom unite use.
In above-mentioned polymkeric substance (2), can comprise with the compound of above-mentioned olefin-copolymerization, for example, the non-conjugated diene compound.The non-conjugated diene compound comprises non-annularity diolefin, alicyclic diolefin etc.These compounds can use separately or two or more being used in combination.
The non-annularity diolefin comprises straight chain non-annularity diolefin, for example 1, and 4-hexadiene, 1,5-hexadiene, 1,6-hexadiene and 1,9-decadiene; With the non-annularity diolefin of side chain 4-methyl isophthalic acid for example, 4-hexadiene, 5-methyl isophthalic acid, 4-hexadiene, 7-methyl isophthalic acid, 6-octadiene, 3,7-dimethyl-1,6-octadiene, 5,7-dimethyl-octa-1,6-diene, 3,7-dimethyl-1,7-octadiene, 7-methyl suffering-1,6-diene and dihydromyrcene.These compounds can use separately or two or more being used in combination.
Alicyclic diolefin comprises tetrahydroindene, methyl tetrahydroindene, Dicyclopentadiene (DCPD), two ring [2.2.1]-heptan-2,5-diene, 5-methylene-2-norbornene, 5-ethylidene alkene-2-norbornylene, 5-propylidene-2-norbornylene, 5-isopropylidene-2-norbornylene, 5-cyclohexylidene-2-norbornylene, 5-vinyl-2-norbornylene etc.These compounds can be used alone or two or more being used in combination.
Mentioned component (A) can be not less than 20% but preferably at room temperature measure degree of crystallinity by X-ray diffraction for crystalline or amorphous.In order to regulate degree of crystallinity, known crystal nucleating agent can be mixed with mentioned component (A).
The fusing point of mentioned component (A) (according to JIS K7121) preferably is not less than 40 ℃.
The molecular weight of mentioned component (A) is not limited especially, but consider that from the viewpoint of forming ability its melt flow rate (MFR) (according to JIS K7210) is preferably 0.001-500g/10min, 0.01-500g/10min more preferably, and then more preferably 0.05-100g/10min, preferably have composition (A) with these value corresponding molecular weight.
Therefore, the above-mentioned polymkeric substance (1) of mentioned component (A) comprises polyethylene (high density polyethylene(HDPE), new LDPE (film grade), chain shaped polyethylene, the catalytic polyethylene of metallocenes etc.), ethylene copolymer (amount that contains ethylene unit based on the monomeric unit total amount accounts for 50 quality % or more multipolymer), ethene-butene-1 copolymer, polypropylene, propylene-ethylene copolymers, propylene copolymer (amount that contains propylene units based on the monomeric unit total amount accounts for 50 quality % or more multipolymer) and poly-1-butylene.In these polymkeric substance, preferably polyethylene, polypropylene and propylene-ethylene copolymers.Propylene-ethylene copolymers comprises random copolymers, segmented copolymer etc., and random copolymers is particularly preferred.These materials can use separately or two or more being used in combination.
The fusing point (according to JIS K7121) of polyethylene mentioned above or ethylene copolymer (for example ethene-alpha-olefin copolymer) preferably is not less than 40 ℃, with and molecular weight be not limited especially, but see that from the viewpoint of forming ability its melt flow rate (MFR) (according to JIS K6922) is preferably 0.001-500g/10min, more preferably 0.01-100g/10min, it is preferred having with these those polymkeric substance that are worth corresponding molecular weight.
Simultaneously, the fusing point (according to JIS K7121) of polypropylene mentioned above or propylene copolymer (for example propylene-alpha-olefin copolymers) preferably is not less than 40 ℃, with and molecular weight be not limited especially, but see that from the viewpoint of forming ability its melt flow rate (MFR) (according to JIS K7210) is preferably 0.01-500g/10min, more preferably 0.05-100g/10min, it is preferred having with these those polymkeric substance that are worth corresponding molecular weight.
The above-mentioned polymkeric substance (2) of mentioned component (A) comprises ethylene-norbornene copolymer, propylene-norbornene copolymer, ethylene-propylene-5-ethylidene-2-norbornene multipolymer etc.These polymkeric substance can use separately or two or more being used in combination.These polymkeric substance are preferably by the catalytic method preparation of metallocenes.The content that constitutes the monomeric unit of the multipolymer of as above mentioning is not limited especially.
When requiring anti-static resin composition of the present invention heat-resisting, preferred component (A) is the combination of polyolefin resin (A-1) and polyolefin resin (A-2), wherein polyolefin resin (A-1) contains cycloalkene unit as constituting monomeric unit and the second-order transition temperature with 60 to 200 ℃, and polyolefin resin (A-2) does not contain cycloalkene unit.In the present invention, said polyolefins resin (A-1) and (A-2) also be called composition (A-1) and (A-2).
The second-order transition temperature of polyolefin resin (A-1) is preferably 60 to 200 ℃, and more preferably 70 to 200 ℃, and then more preferably 70 to 190 ℃, preferred especially 75 to 185 ℃.When second-order transition temperature was too low, it was not enough to give stable on heating effect; When it is too high, may make the appearance variation of moulded product.In order to obtain to have the polymkeric substance of above-mentioned second-order transition temperature,, be the scope of 40 to 90 quality % preferably by the cycloolefin of copolymerization with respect to the total amount of composition (A-1).
Second-order transition temperature can be measured by conventional method, for example uses differential scanning calorimetry (DSC).
The melt flow rate (MFR) of polyolefin resin (A-1) (measuring according to ISO1133 load 2.16kg under 260 ℃ of temperature) preferred 0.1 is to 100ml/10min.
And preferred polyolefm resin (A-1) is unbodied.
As the polyolefin resin (A-2) that is used in combination with polyolefin resin (A-1), can use except containing cycloalkene unit as all mentioned components (A) that constitute monomeric unit, therefore the description about composition (A) also is effective to polyolefin resin (A-2).
When the total amount of said polyolefins resin (A-1) and polyolefin resin (A-2) is 100 quality %, their mixture ratio is the composition (A-1) of 1-95 quality % and the composition (A-2) of 99-5 quality %, the composition (A-1) of preferred 10-90 quality % and the composition (A-2) of 90-10 quality %, the more preferably composition (A-2) of the composition of 20-80 quality % (A-1) and 80-20 quality %, the composition (A-1) of preferred especially 40-80 quality % and the composition (A-2) of 60-20 quality %.By using these resins that are used in combination to demonstrate good thermotolerance and moulded product outward appearance in above-mentioned scope separately.
In anti-static resin composition of the present invention, the content of composition (A) is 30-95 quality %, preferred 42-92 quality %, further preferred 49-92 quality %, preferred especially 49-90 quality %, condition is that the total amount of composition (A), composition (B) and composition (C) is 100 quality %.When content during less than 30 quality %, hardness trends towards variation; When surpassing 95 quality %, anti-static function trends towards variation.
1-2. composition (B)
Composition of the present invention (B) is a segmented copolymer, and it comprises olefin polymer block (being also referred to as " polymer blocks (b1) " in the present invention) and hydrophilic polymer block (being also referred to as " polymer blocks (b2) " in the present invention).Composition (B) can provide anti-static resin composition of the present invention with anti-static function.Can be used alone the combination of composition (B) or two or more compositions (B).
In mentioned component (B), polymer blocks (b1) and arrangement (b2) are not limited especially, can have the block structure by the explanation of following (1) to (5) example.Here, m1 is 1 or bigger integer, and m2 and m2 ' are 2 or bigger integer, can be for identical or different.When being a plurality of when polymer blocks (b1) in each structure and (b2), each block can be for identical or different.
(1)(b1-b2)
m1
(2)b1-(b2-b1)
m1
(3)b2-(b1-b2)
m1
(4)(b1)
m2-(b2)
m2’
(5)b1-b1-(b2-b2-b1-b1)
m1
Wherein, preferred block structure (1), (2) and (3), i.e. polymer blocks (b1) and alternately multiple block structure (b2).
Composition (B) mainly is made of the segmented copolymer of as above mentioning, but for example polyamide-block and polyester block can be to account for 20 quality % or ratio still less is introduced in composition (B) for other (being total to) polymer blocks.
At above-mentioned block structure (1) in (5), preferred polymers block (b1) and (b2) between mode of connection be ester bond, amido linkage, ehter bond, urethane bond or imide bond.
Polymer blocks (b1) is the block that is made of the polymkeric substance that mainly comprises olefin unit, and the compound that forms this polymkeric substance comprises, for example has the non-cyclic olefin class and the cyclenes hydro carbons of 2 or more carbon atoms.The example of non-cyclic olefin class comprises ethene and alpha-olefin for example propylene, 1-butylene, 1-amylene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene and 3-methyl hexene-1.The example of cyclenes hydro carbons comprises norbornylene etc.These compounds can use separately or two or more are used in combination.
Polymer blocks (b1) can be for containing for example 4-methyl isophthalic acid of non-conjugated diene except that above-claimed cpd, 4-hexadiene, 5-methyl isophthalic acid, and 4-hexadiene, 7-methyl isophthalic acid, 6-octadiene and 1, the 9-decadiene is as the polymkeric substance that constitutes monomeric unit.
For make polymer blocks (b1) and (b2) between mode of connection be ester bond, amido linkage, ehter bond, urethane bond or imide bond, molecule two ends of above-mentioned polymer blocks (b1) are preferably carboxyl, hydroxyl, amino, anhydride group, oxazolinyl, epoxide group etc.Provide the method for these functional groups to comprise, for example wherein will have the method that the carbon-to-carbon unsaturated compound of as above mentioning functional group and the heat-degradation polymer that has carbon-to-carbon double bond in molecular end carry out addition reaction.
The number-average molecular weight of above-mentioned polymer blocks (b1) is measured by gel permeation chromatography (GPC), is scaled polystyrene, is preferably 800-20000, and more preferably 1,000-10,000 and further preferred 1,200-6,000.
In mentioned component (B), can contain separately the combination of one or both or multiple polymers block (b1).
Above-mentioned polymer blocks (b2) is by having for example block that constitutes of the polymkeric substance of hydroxyl, amino and ether of hydrophilic radical, preferably being made of the polymkeric substance that has ehter bond on main chain.This polymkeric substance comprises polyethers (b2-a), contains the hydrophilic polymer (b2-b) and the anionic polymer (b2-c) of polyethers.
Polyethers (b2-a) comprises polyether glycol, polyether diamine and its modified product.
The hydrophilic polymer (b2-b) that contains polyethers comprises the polyether ester amides with polyether glycol chain link, the polyetheramides imide with polyether glycol chain link, the polyether ester with polyether glycol chain link, has the polyetheramides of polyether diamine chain link and have polyether glycol or the polyether(poly)urethane of polyether diamine chain link.
Anionic polymer (b2-c) comprises that anionic polymer, anionic polymer comprise dicarboxylic acid and polyethers (b2-a) with alkylsulfonyl and preferably have 2 to 80 as the neccessary composition unit and in its molecule, more preferably 3 to 60 alkylsulfonyls.
These polymkeric substance can be for straight or branched.In addition, polymer blocks (b2) can only be made of maybe a kind of block and can comprise two or more blocks.Preferred component (b2) is polyethers (b2-a), preferred, polyethers two pure and mild polyetheramines, special preferred, polyethers glycol.
Comprise that as the polyether glycol of polyethers (b2-a) those are by general formula (1):
H-(OA
1)
n-O-E
1-O-(A
1O)
n’-H
The compound of expression
With those by general formula (2):
H-(OA
2)
m-O-E
2-O-(A
2O)
m’-H
The compound of expression.
In general formula (1), E
1The residue that hydroxyl obtains, A are removed in expression from the compound that contains hydroxyl of binary
1For having the alkylidene group of 2 to 4 carbon atoms, n and n ' represent the number of the epoxy alkane addition of each hydroxyl in the compound that contains hydroxyl of above-mentioned binary separately.Unitary (the OA of n
1) and the unitary (A of n '
1O) can be for identical or different, when it was made of two or more alkylidene oxides, group can be bonded with block, mode random or combination.In general, n and n ' be 1 to 300, preferred 2 to 250, preferred especially 10 to 100 integer.And n and n ' can be for identical or different.
The compound of the hydroxyl of above-mentioned binary is included in the compound that contains two alcoholic extract hydroxyl groups or phenolic hydroxyl group in a part, that is, dihydroxy compound is in particular the glycol of dibasic alcohol, dihydric phenol and tertiary-amino-containing.These compounds can use separately or two or more are used in combination.
Dibasic alcohol can be for any aliphatic, alicyclic and fragrant type, and preferred compound has 2 to 12 carbon atoms.
The example of aliphatic dihydroxy alcohol comprises aklylene glycol, and for example ethylene glycol, propylene glycol for example 1, ammediol, 1,4-butanediol, 1,6-hexane diol, 1,9-nonane glycol, dimethyltrimethylene glycol, 1,12-dodecanediol etc.
The example of alicyclic dibasic alcohol comprises 1,2-and 1,3-pentamethylene glycol, 1,2-, 1,3-and 1,4-cyclohexane diol, 1,4 cyclohexane dimethanol etc.
The example of aromatic diols comprises xylyl alcohol etc.
The example of dihydric phenol comprises, many rings binary phenol of monocycle binary phenol, bis-phenol and condensation for example, and preferred compound has 6 to 18 carbon atoms.
Monocycle binary phenol comprises for example Resorcinol, catechol, Resorcinol and laccol.
Bis-phenol for example comprise dihydroxyphenyl propane, Bisphenol F, bisphenol S, 4,4 '-dihydroxyl phenylbenzene-2,2-butane, dihydroxybiphenyl and dihydroxydiphenyl ether.
Many rings dihydric phenol of condensation comprises for example dihydroxy naphthlene and dinaphthol.
And the glycol that contains uncle's amino comprises N-alkyl two alkanolamines that for example have 1 to 8 carbon atom.
In general formula (2), E
2Expression is removed the residue that hydroxyl obtains, A from containing of the binary mentioned in the oxy-compound general formula (1)
2For at least a portion is by general formula (3) :-CHR-CHR '-(wherein a kind of of R and R ' is by general formula (4) :-CH
2O (A
3O)
xR " group of expression, other be H, in general formula (4), x is 1 to 10 integer, R " and be H or alkyl, aryl, alkylaryl, arylalkyl or acyl group with 1 to 10 carbon atom, A
3For having the alkylidene group of 2 to 4 carbon atoms) substituted alkylene of expression, simultaneously remaining A
2Can be for having the alkylidene group of 2 to 4 carbon atoms.Unitary (the OA of m
2) and the unitary (A of m '
2O) can be for identical or different.Preferred m and m ' be 1 to 300, further preferred 2 to 250, preferred especially 10 to 100 integer.And m and m ' can be for identical or different.
Polyether glycol by above-mentioned general formula (1) expression can be by the addition reaction preparation that contains oxy-compound of epoxy alkane and binary.As epoxy alkane, use epoxy alkane to comprise for example oxyethane, propylene oxide, 1 with 2 to 4 carbon atoms, 2-butylene oxide ring, 1,4-butylene oxide ring, 2,3-butylene oxide ring and 1, the 3-butylene oxide ring, with and two or more combination.When using two or more epoxy alkane, they can be bonded with any random and/or block fashion.Preferred epoxy alkane only is an oxyethane, and the combination of oxyethane and other epoxy alkane can add with block and/or random fashion.The number that each hydroxyl of the hydroxy-containing compounds of above-mentioned binary is added into epoxy alkane is preferably 1 to 300, more preferably 2 to 250, not preferred 10 to 100 integer.
Comprise following method (I) and (II) by the polyether glycol preparation method's of above-mentioned general formula (2) expression preferred embodiment.
(I) carry out polymerization with the compound that contains hydroxyl of above-mentioned binary as raw material and glycidyl ether in the method by general formula (5) expression:
(in general formula (5), A
4For having the alkylidene group of 2 to 4 carbon atoms, p is 1 to 10 integer, R
1For H or have alkyl, aryl, alkylaryl, arylalkyl or the acyl group of 1 to 10 carbon atom), optional and epoxy alkane copolymerization with 2 to 4 carbon atoms.
(II) use the compound that contains hydroxyl of binary to prepare polyether glycol by the polyethers that on side chain, has chloromethyl in the method as raw material.More specifically, by Epicholorohydrin or Epicholorohydrin and epoxy alkane addition (being total to) polymerization are obtained the polyethers that side chain has chloromethyl, then by with polyethers and polyalkylene glycol and R with 2 to 4 carbon atoms
1X (R wherein
1As indicated above, represent chlorine, bromine or iodine with X) in the presence of alkali, react, or polyethers and the polyalkylene glycol mono carbyl ether (polyalkylene glycolmonocarbyl ether) with 2 to 4 carbon atoms reacted in the presence of alkali and prepare polyether glycol.
As 2 to 4 the former epoxy alkane of carbon that have that use herein, all are above-described all can use.
As above-mentioned polyether diamine, can use the polymkeric substance that adopts conventional method to form replacing with amino by the hydroxyl in the polymkeric substance of above-mentioned general formula (1) expression.
The compound of above-mentioned polyetheramides for constituting by polymeric amide and polyether diamine.
The above-mentioned polyetheramides imide compound that polyamidoimide with at least one imide ring and polyether glycol constitute of serving as reasons.
The compound of above-mentioned polyether ester for constituting by polyester and polyether glycol.
The above-mentioned polyether ester amides compound that the polymeric amide that has carboxyl endways and polyether glycol constitute of serving as reasons.
Above-mentioned polyether(poly)urethane is for by organic diisocyanate and polyether glycol or the compound that is made of organic vulcabond, polyether diamine and chain propagation agent.
Above-mentioned anionic polymer (b2-c) can obtain by the above-mentioned polymer blocks of modification; for example; by the block that will constitute by polyether glycol and/or polyether diamine; with the unit copolymerization that constitutes by dicarboxylic acid with alkylsulfonyl; acquisition has 2 to 80 in molecule, the polymkeric substance of preferred 3 to 60 alkylsulfonyls.
For further improving purpose, at least a salt (H) that is selected from basic metal and alkaline-earth metal can be incorporated in the composition (B) as the anti-static function of target of the present invention.This composition can be introduced between composition (B) polymerization period or after composition (B) polymerization before composition (B) polymerization.And this composition can also be introduced during resin combination preparation of the present invention, or is introduced in the mode of aforesaid method combination.
Composition (H) comprises for example for example salt and the halides of magnesium and calcium and organic acid, sulfonic acid or mineral acid of lithium, sodium and potassium and/or alkaline-earth metal of basic metal.
Composition (H) more preferred example comprises alkali-metal halides for example lithium chloride, sodium-chlor, Repone K, lithiumbromide, Sodium Bromide and Potassium Bromide; Alkali-metal inorganic acid salt is lithium perchlorate for example, sodium perchlorate and potassium perchlorate; Alkali-metal organic acid salt is potassium acetate and lithium stearate for example; Alkylsulphonic acid with 8 to 24 carbon atom alkyls is an alkali metal salt of octyl group sulfonic acid, dodecyl sodium sulfonate, tetradecyl sulfonic acid, octadecyl sulfonic acid, tetracosyl sulfonic acid and 2-ethylhexyl sulfonic acid for example; Aromatic sulphonic acid is an alkali metal salt of phenylbenzimidazole sulfonic acid and naphthyl sulfonic acid for example; Alkyl benzene sulphonate (ABS) with 6 to 18 carbon atom alkyls is an alkali metal salt of octyl phenyl sulfonic acid, dodecylphenyl sulfonic acid, dibutyl phenylbenzimidazole sulfonic acid and dinonyl phenylbenzimidazole sulfonic acid for example; Alkyl naphthalene sulfonic acid with 2 to 18 carbon atom alkyls is an alkali metal salt of dimethyl naphthyl sulfonic acid, di-isopropyl naphthyl sulfonic acid and dibutyl naphthyl sulfonic acid for example; Fluoro sulfonic acid is an alkali metal salt etc. of trifluoromethayl sulfonic acid for example.These materials can use separately or two or more are used in combination.With respect to composition of the present invention (B), mentioned component (H) can preferably use with 0.001 to 10 quality % and further preferred 0.01 to 5 quality % scope.
Composition of the present invention (B) by the polymer blocks of as above mentioning (b1) and (b2) with above-mentioned block structure (1) to (5), the arrangement that preferred block structure (1) to (3) shows constitutes.
Polymer blocks (b1) and component ratio (b2) (b1)/(b2), when these total amounts are assumed to 100 quality %, preferred 10-90 quality %/10-90 quality %, more preferably 20-80 quality %/20-80 quality % and further preferred 30-70 quality %/30-70 quality %.
When mentioned component (B) had the arrangement of block structure (2) or (3), polymer blocks (b1) and average repeat number (b2) were preferably 2 to 50.
Mentioned component (B) can be by with the method polymerization acquisition with routine of above-mentioned olefin polymer block (b1) and above-mentioned hydrophilic polymer block (b2).For example, can be by under reduced pressure preparing 200 to 250 ℃ of polyreactions of carrying out polymer blocks (b1) and polymer blocks (b2).In addition, can use conventional polymerizing catalyst during the polyreaction.
Preferred following one or both or multiple combination of operable conventional polymerizing catalyst during polyreaction: the catalyzer of tin class is catalyzer for example catalyzer for example catalyzer for example zirconium hydroxide, zirconium white and zirconium acetate and the IIB family organic salt catalyzer of tetrabutyl titanate ester, zirconium class of ANTIMONY TRIOXIDE SB 203 99.8 PCT and tellurium dioxide, titanium class of monobutyltin oxide, antimony class for example.
In addition, mentioned component (B) can be by the method preparation of for example describing in TOHKEMY 2001-278985, TOHKEMY 2003-48990 etc.
As composition (B), can use commercially available product, for example Sanyo ChemicalIndustries company " PELESTAT " series 300,303,230 of producing etc. is suitable.
The total amount of supposing composition (A), composition (B) and composition (C) is 100 quality %, the content of composition (B) in anti-static resin composition of the present invention is 5 to 20 quality %, preferred 8 to 18 quality %, more preferably 8 to 16 quality % and preferred especially 10 to 16 quality %.When content during less than 5 quality %, anti-static function trends towards variation; When surpassing 20 quality %, the appearance of moulded product trends towards variation.
1-3. composition (C)
Composition of the present invention (C) is at least a polymkeric substance of the hydrogenated products (also being referred to as " polymkeric substance (C2) " in the present invention) that is selected from the polymkeric substance that comprises conjugated diene compound unit (also being referred to as " polymkeric substance (C1) " in the present invention) and described polymkeric substance (C1).
Above-mentioned polymkeric substance (C1) can be for only comprising the unitary polymkeric substance of conjugated diene compound, or comprise described conjugated diene compound unit and the unitary polymkeric substance of aromatic ethenyl compound.
Constitute the unitary conjugated diene compound of above-mentioned conjugated diene compound and comprise, for example 1,3-butadiene, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene and 1,3-pentadiene.These compounds can use separately or two or more are used in combination.Wherein, 1,3-butadiene and isoprene are preferred.Therefore, only comprise the unitary polymkeric substance of above-mentioned conjugated diene compound (C1) and comprise polyhutadiene and polyisoprene.
Constitute the unitary aromatic ethenyl compound of above-mentioned aromatic ethenyl compound and comprise, for example vinylbenzene, alpha-methyl styrene and hydroxy styrenes.These compounds can use separately or two or more are used in combination.Wherein, vinylbenzene and alpha-methyl styrene are preferred, and vinylbenzene is particularly preferred.
When above-mentioned polymkeric substance (C1) comprised conjugated diene compound unit and aromatic ethenyl compound unit, each compound unit can be only be made of or two or more constitute a kind of.
The unitary content of above-mentioned conjugated diene compound in above-mentioned polymkeric substance (C1), when supposing that conjugated diene compound unit and aromatic ethenyl compound unit total amount are 100 quality %, preferred 30 to 95 quality %, more preferably 50 to 95 quality % and preferred especially 60 to 93 quality %.Simultaneously, the unitary content of above-mentioned aromatic ethenyl compound in above-mentioned polymkeric substance (C1), when supposing that conjugated diene compound unit and the unitary total amount of aromatic ethenyl compound are 100 quality %, preferred 5 to 70 quality %, more preferably 5 to 50 quality % and preferred especially 7 to 40 quality %.
Based on the monomeric unit of all formation polymkeric substance (C1), the preferred 80 quality % or more of the unitary total amount of above-mentioned conjugated diene compound unit and aromatic ethenyl compound, more preferably 90 quality % or more.
When above-mentioned polymkeric substance (C1) contains conjugated diene compound unit and aromatic ethenyl compound unit, described polymkeric substance (C1) can further contain can with other unit of the compound of aromatic ethenyl compound and conjugated diene compound copolymerization.Such unit can be only be made of or two or more constitute a kind of.
Above-mentioned polymkeric substance (C1) can be segmented copolymer or random copolymers, and in addition, it can be random copolymers and segmented copolymer mixed form.These polymkeric substance can use separately or two or more are used in combination.Wherein, segmented copolymer is preferred.
When above-mentioned polymkeric substance (C1) contains conjugated diene compound unit and aromatic ethenyl compound unit, preferably comprise mainly by the conjugated diene compound unit (with respect to the preferred 80 quality % or more of all monomeric units, more preferably 90 quality % or more, with further preferred 99 quality % or more) segmented copolymer of the polymer blocks (c1) that constitutes and the polymer blocks (c2) that mainly constitutes by aromatic ethenyl compound unit (with respect to the preferred 80 quality % or more of all monomeric units).Above-mentioned polymer blocks (c1) and above-mentioned polymer blocks (c2) can contain above-mentioned aromatic ethenyl compound unit and above-mentioned conjugated diene compound unit respectively.
Above-mentioned polymer blocks (c1) contains vinyl bonds usually, and its content (total amount) is not limited especially.That is, it can be 50% or more, maybe can be for less than 50%.Under the situation in front, in polymer blocks (c1), be generally 50-95%.Under the situation of back, it is easy that the hardness of moulded product and transparency are regulated transfiguration.
When polymer blocks (c2) contained the conjugated diene compound unit, it can contain ethylenic linkage.
Above-mentioned polymer blocks (c1), particularly when it contains two or more conjugated diene compound unit, the block that can be bonded with any form of random, block and alternation block for the unit.Polymer blocks (c1) can contain 1 to 10 unitary alternation block, and wherein the aromatic ethenyl compound unit little by little increases, or can suitably contain from the mutual different polymer blocks of the unitary ethylenic linkage content of conjugated diene compound.
Above-mentioned polymkeric substance (C1) is well-known in the anionic polymerization field, and is for example, open in the clear 47-28915 of the patent publications Nos. of Japan, clear 47-3252, clear 48-2423 and clear 48-20038.Preparation method with polymkeric substance of alternation block discloses in Japanese kokai publication sho 60-81217.
The content (1 of vinyl bonds in above-mentioned polymer blocks (C1), 2-and 3, the 4-linkage content) regulate and can finish by using following material: amine is N for example, N, N ', N '-Tetramethyl Ethylene Diamine, Trimethylamine, triethylamine, diazonium heterocycle (2,2,2) octane, ether is the alkoxide etc. of tetrahydrofuran (THF), diethylene glycol dimethyl ether, Diethylene Glycol dibutyl ether, thioether, phosphine, phosphamide, benzene sulfonamide acid esters, potassium and sodium for example.
Also can use after obtaining polymkeric substance and molecular chain be prolonged or the branch branched polymers by the residue that uses coupler by aforesaid method.The coupler of Shi Yonging comprises herein, for example diethylene adipate, Vinylstyrene, dimethyl dichlorosilane (DMCS), silicon tetrachloride, butyl trichlorosilicane, tin tetrachloride, butyl tin trichloride, dimethyl chlorination silicon, germanium tetrachloride, 1,2-ethylene dibromide, 1,4-chloromethylbenzene, two (Trichloromonosilane base) ethane, epoxidised Toenol 1140, tolylene diisocyanate and 1,2,4-benzene triisocyanate.
Preferably the scope from vinyl bonds (1,2-and 3, the 4-key) content of the conjugated diene compound of above-mentioned polymkeric substance (C1) is 5 to 80%.The number-average molecular weight of above-mentioned polymkeric substance (C1) is preferably 10,000 to 1,000,000, and is further preferred 20,000 to 500,000, and further more preferably 20,000 to 300,000, preferred especially 20,000 to 200,000.Number-average molecular weight is measured by gel permeation chromatography (GPC), below this point all identical.
Preferred block copolymer as above-mentioned polymkeric substance (C1) comprises the polymkeric substance that has by the structure of following formula (IV)-(XI) expression.
(C
1-C
2)
y (IV)
(C
1-C
2)
y-X (V)
(C
2-C
1)
z-C
2 (VI)
(C
2-C
11-C
12)
y (VII)
(C
11-C
12)
Z (VIII)
(C
11-C
12)
Z-X (IX)
(C
12-C
11-C
12)
Z′ (X)
(C
12-C
11-C
12)
Z′-X (XI)
(in various, C
1Be the polymer blocks that only constitutes, or mainly comprise the conjugated diene compound unit and further comprise the polymer blocks of aromatic ethenyl compound unit etc., C by unitary homopolymer of conjugated diene compound or multipolymer
2For mainly comprising the unitary polymer blocks of aromatic ethenyl compound,, can contain conjugated diene compound as a part as long as it is the polymer blocks that comprises aromatic ethenyl compound basically.Preferably contain 90 quality % or more, further preferred 99 quality % or more aromatic ethenyl compound.X is the residue of coupler, C
11Conjugated diene compound is unitary in order mainly to comprise, vinyl bonds content is 20% or more polymer blocks, C
12Conjugated diene compound is unitary in order mainly to comprise, vinyl bonds content is less than 20% polymer blocks, and y is 1 to 5 integer, and Z is 1 to 5 integer, and Z ' is 1 to 5 integer.In various, when there being a plurality of C
1The time, they can be for identical or different.C
2Also be like this.)
Scope from vinyl bonds (1,2-and 3, the 4-key) content of conjugated diene compound in the preferred block copolymer of above-mentioned polymkeric substance (C1) is preferably 5 to 80%, the number-average molecular weight of described segmented copolymer is preferably 10,000 to 1,000,000, further preferred 20,000 to 500,000, preferred especially 20,000 to 300,000.In above-mentioned formula (IV) in (XI), polymer blocks C
1(C
11And C
12) number-average molecular weight be preferably 5,000 to 200,000, polymer blocks C
2Number-average molecular weight be preferably 3,000-150,000.
The ratio ranges of aromatic ethenyl compound and conjugated diene compound is preferably aromatic ethenyl compound/conjugated diene compound=10-70/30-90 quality % in the preferred block copolymer of above-mentioned polymkeric substance (C1), further preferred 15-65/35-85 quality %, preferred especially 20-60/40-80 quality %.
In above-mentioned segmented copolymer, see that from the viewpoint that influences shock-resistance preferred polymkeric substance contains the polymkeric substance of the alternation block that 1 to 10 unit aromatic ethenyl compound little by little increases for block (c2) wherein, and/or those radial block type polymers of having handled through couplings.
As above-mentioned polymkeric substance (C1), can use commercially available product, for example " TR2000 ", " TR2500 ", " TR2600 ", " TR2827 " (trade name) of the production of JSR company.
On the other hand, polymkeric substance (C2) is the hydrogenated products of above-mentioned polymkeric substance (C1).In other words, the polymkeric substance that has been hydrogenated from the unitary carbon-to-carbon double bond of conjugated diene compound at least a portion of above-mentioned polymkeric substance (C2).Hydrogenation ratio is preferred 10 to 100%, and more preferably 50 to 100%, preferred especially 90 to 100%.
As above-mentioned polymkeric substance (C2), can use one or more hydrogenated products of the polymkeric substance with above-mentioned formula (IV) to (XI) expression structure.As the polymkeric substance that will be hydrogenated (C1), the polymkeric substance of formula (VI) expression is particularly preferred, wherein polymer blocks C
1Those of vinyl bonds content 60 to 90% be preferred, wherein content 70 to 85% those be particularly preferred.
The hydrogenation of above-mentioned polymkeric substance (C1) can be finished by the method for routine, for example the clear 42-8704 of the patent disclosure No. of Japan, Japan the clear 43-6636 of patent disclosure No., Japan the clear 63-4841 of patent disclosure No., Japan the clear 63-5401 of patent disclosure No., Japanese kokai publication hei 2-133406 and Japanese kokai publication hei 1-297413 in disclosed method.
As above-mentioned polymkeric substance (C2), can use commercially available product, for example " DYNARON 1320P ", " the DYNARON 1321P ", " DYNARON 2324P ", " DYNARON 6200P ", " the DYNARON 4400P " and " DYNARON 4600P " that produce of JSR company and " TUFTEC H1041 " (all being trade(brand)name) that can use the production of Asahi chemical industrial company.
The melt flow rate (MFR) of mentioned component (C) (measuring under 230 ℃ of temperature, 2.16kg load according to ASTM D1238) all is preferably 0.5 to 50g/10min at above-mentioned two kinds of polymkeric substance (C1) with (C2), and more preferably 1 to 20g/10min.
Above-mentioned polymkeric substance (C1) and (C2) can make up as mentioned component (C) and use.
Preferably only use above-mentioned polymkeric substance (C2), or make up above-mentioned polymkeric substance (C1) and (C2) use as composition (C).Preferably (C1)/(C2) ratio is 0-80 quality %/100-20 quality %, more preferably 0-60 quality %/100-40 quality % and further preferred 0-40 quality %/100-60 quality %.
The total amount of supposing composition (A), composition (B) and composition (C) is 100 quality %, the content of the composition in anti-static resin composition of the present invention (C), preferred 0 to 50 quality %, more preferably 0 to 40 quality % and preferred especially 0 to 35 quality %.When this content surpassed 50 quality %, hardness trended towards descending, and particularly when being used as the supporter of pressure-sensitive adhesive film, film lacks hard sensation.
1-4. other composition
Anti-static resin composition of the present invention can further contain at least a antistatic activator (E) (being called " composition (E) " in the present invention), and it is selected from by following ingredients (E1), composition (E2), composition (E3) and composition (E4).These compositions can be used alone or be used in combination.
Composition (E1): have the salt that anionicsite comprises the fluoro-alkyl alkylsulfonyl;
Composition (E2): comprise by following general formula (XII) and represent unitary polymkeric substance;
Composition (E3): comprise by following general formula (XIII) and represent unitary boron compound; With
Composition (E4): non-ionic tensio-active agent.
(R wherein
5The expression alkyl, preferred alkylidene group, and R
5 'The expression hydrogen atom, halogen atom or alkyl, X represents hydrogen atom, alkyl, has the alkyl or the hydrophilic group of carbamate residue or ester residue, the hydrophilic group of preferred anionic, m represent 1 or bigger number)
Have salt (E1) (also being referred to as " composition (E1) " in the present invention) that anionicsite comprises fluoro-alkyl alkylsulfonyl mentioned above and mean the salt that comprises anionicsite with one or more fluoro-alkyl alkylsulfonyls and suitable cationic moiety.The number of fluorine atoms that is bonded on the carbon atom of fluoro-alkyl alkylsulfonyl is not limited especially, can be that 1 to 3 fluorine atom is bonded to carbon atom.The quantity of alkylsulfonyl is not limited especially.
Be included in the fluoro-alkyl alkylsulfonyl example in the anionicsite, comprise fluoro low alkyl group alkylsulfonyl for example trifluoromethayl sulfonic acid, pentafluoride ethane sulfonic acid, particularly perfluoroalkyl alkylsulfonyl.The negatively charged ion of moiety (E1) comprises except that trifluoromethayl sulfonic acid itself; the derivative of methide, ammonia etc. etc.; wherein hydrogen atom is by one or more; preferred a plurality of trifluoromethane sulfonyl group replaces, for example two (trifluoromethane sulfonyl group) imides, three (trifluoromethane sulfonyl group) methide etc.Anionicsite can comprise CF particularly
3SO
3 -, (CF
3SO
2)
2N
-, (CF
3SO
2)
3C
-Deng.Cationic moiety can comprise for example Li of alkalimetal ion
+, Na
+And K
+, wherein, Li
+Be preferred.
Therefore, composition (E1) can comprise trifluoromethayl sulfonic acid lithium, two (trifluoromethane sulfonyl group) imidization lithium, two (trifluoromethane sulfonyl group) imidization sodium, two (trifluoromethane sulfonyl group) imidization potassium, three (trifluoromethane sulfonyl group) lithium, three (trifluoromethane sulfonyl group) sodium methylate, three (trifluoromethane sulfonyl group) potassium etc. that methylates that methylates.These compositions can use separately or two or three be used in combination.Wherein, trifluoromethayl sulfonic acid lithium, two (trifluoromethane sulfonyl group) imidization lithium and three (trifluoromethane sulfonyl group) lithium that methylates is preferred.
When using mentioned component (E1), it can just use with itself, or can be it is dissolved in for example form of the solution in water, two [2-(2-butoxy oxyethyl group) ethyl] adipic acid ester and two (2-butoxyethyl group) phthalic esters of solvent, or its can be in advance with the polymkeric substance with ehter bond for example mentioned component (B) mix, use with the form of masterbatch (mastbach) etc.The segmented copolymer that other example with polymkeric substance of ehter bond comprises polyoxyethylene glycol, polyoxyethylene, be made of polyamide-block and polyoxyethylene glycol block, segmented copolymer of constituting by polyester block and polyoxyethylene glycol block etc.When composition (E1) is dissolved, preferred 0.1 to the 80 quality % of concentration range, further preferred 1 to 60 quality %.
As mentioned component (E1), can use commercially available product.For example, can use those with the solution form, comprise " SANKONOL0862-20R ", " SANKONOL 0862-13T ", " SANKONOL 0862-10T ", " SANKONOLAQ-50T " (all being trade(brand)name) of preparations such as Sanko chemistry company limited.As those compositions (E1), can use " SANKONOL TBX-25 " (trade(brand)name) of preparation such as Sanko chemistry company limited with master batch form.
Can use separately the mentioned component (E1) of one or both or multiple combination.
When only composition (E1) is as composition (E), when composition (A), (B) and total amount (C) are assumed to 100 quality %, preferred 0.01 to the 30 quality % of the content of composition in anti-static resin composition of the present invention (E), more preferably 0.01 to 20 quality %, further preferred 0.1 to 10 quality % and preferred especially 0.1 to 5 quality %.When composition (E1) content when being excessive, the appearance poor of moulded product sometimes under this situation; When content was too low, sometimes antistatic to improve effect not enough.
Comprise by above-mentioned general formula (XII) and represent that unitary polymkeric substance (E2) (being also referred to as " composition (E2) " in the present invention) is to comprise preferred 10 to 100 quality %, more preferably 20 to 100 quality %, the further described unitary polymkeric substance of preferred 30 to 100 quality %.When this unit ratio was too low, the improvement of anti-static function sometimes can not fully show, but character intensity variation for example.
The amount that said units preferably contains in polymkeric substance constituent (E2) is Unit at least 2 or more, preferred Unit 3 to 30.
In above-mentioned general formula (XII), R
5Be alkyl, preferably have the alkylidene group of 2 to 4 carbon atoms, preferred especially ethylidene.
In above-mentioned general formula (XII), R
5 'Be hydrogen atom, halogen atom or alkyl.Halogen atom comprises chlorine atom, bromine atoms, iodine atom etc.Alkyl comprises for example alkyl, alkenyl, aryl, cycloalkyl and cycloalkenyl group.The carbon atom number is not limited especially in these groups.
Alkyl comprises for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, tert-pentyl, n-hexyl, Sec-Hexyl, n-heptyl, Zhong Gengji, n-octyl, the 2-ethylhexyl, secondary octyl, n-nonyl, Zhong Renji, positive decyl, secondary decyl, the n-undecane base, secondary undecyl, dodecyl, secondary dodecyl, the n-tridecane base, isotridecyl, secondary tridecyl, the n-tetradecane base, secondary tetradecyl, n-hexadecyl, secondary hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, tricosyl, the 2-butyl octyl, 2-butyl decyl, 2-hexyl octyl group, the 2-hexadecyl, the 2-octadecyl, 2-hexyl dodecyl, 2-octyl group dodecyl, 2-decyl tetradecyl, 2-dodecyl hexadecyl, the 2-cetostearyl, 2-tetradecyl octadecyl and monomethyl side chain-the isooctadecane base.
Alkenyl comprises for example vinyl, allyl group, propenyl, butenyl, isobutenyl, pentenyl, isopentene group, hexenyl, heptenyl, octenyl, nonene base, decene base, undecenyl, dodecenyl succinic, tetradecene base and oleyl.
Aryl comprises for example phenyl; tolyl; xylyl; cumyl; Lai Ji; benzyl; styroyl; styryl; cinnamoyl; diphenyl-methyl; trityl; ethylphenyl; the propyl group phenyl; butyl phenyl; the amyl group phenyl; the hexyl phenyl; the heptyl phenyl; octyl phenyl; the nonyl phenyl; decyl phenyl; the undecyl phenyl; dodecylphenyl; phenyl; benzyl phenyl; the phenyl of styrylization; to the cumyl phenyl; the dinonyl phenyl; Alpha-Naphthyl and betanaphthyl.
Cycloalkyl comprises for example cyclopentyl, cyclohexyl, suberyl, methylcyclopentyl, methylcyclohexyl and methyl suberyl.
Cycloalkenyl group comprises for example cyclopentenyl, cyclohexenyl, cycloheptenyl, methyl cyclopentene base, methyl cyclohexane thiazolinyl and methyl cycloheptenyl.
From with the Combination of resin and the viewpoint of consistency, R
5 'Be preferably hydrogen atom, halogen atom and have the alkyl of 1 to 36 carbon atom, more preferably hydrogen atom, chlorine atom, bromine atoms, have the alkyl of 1 to 24 carbon atom and have the aryl of 2 to 24 carbon atoms.
X is hydrogen atom, alkyl, has the alkyl or a hydrophilic group (for example anionic hydrophilic group) of carbamate residue or ester residue in above-mentioned general formula (XII).
Alkyl can be as above R
5 'The alkyl of mentioning promptly can comprise alkyl, alkenyl, aryl, cycloalkyl, cycloalkenyl group etc.Wherein, the alkyl with 1 to 6 carbon atom is preferred, and the alkyl with 1 to 4 carbon atom is most preferred.
The carbamate residue means the atomic radical of monoisocyanates, and wherein isocyanic ester is reacted.Above-mentioned monoisocyanates comprises for example methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, hexyl isocyanate, octyl isocyanate, isocyanic acid dodecane ester, isocyanic acid octadecane ester, NSC 87419, phenylcarbimide, tolyl isocyanic ester and oleyl isocyanic ester.
Ester group in the alkyl with ester residue comprises, for example ethanoyl, propionyl, butyryl radicals, isobutyryl, pentanoyl, isovaleryl, valeryl, lauroyl, myristoyl, palmitoyl, stearyl-, docosyl, acryl, propioloyl, methacryloyl, crotonyl, oleoyl, benzoyl, phthaloyl and succinyl.
Anionic hydrophilic group comprises, for example alkane sulfonate group-C
kH
2kSO
3M (wherein k is 2 to 4 integer), sulfuric acid alkali-SO
3M, phosphate base-PO
3M
2With methyl carboxylic acids alkali-CH
2COOM.
M in each group is hydrogen atom, atoms metal or ammonium (comprising quaternary ammonium salt).
When M was atoms metal, its example comprised alkali metal atom for example lithium, sodium and potassium; With alkaline earth metal atom for example magnesium and calcium (being 1/2 under the alkaline earth metal atom situation) because they are generally divalence.Wherein, sodium and potassium are preferred.
When M is ammonium, ammonium forms material and comprises for example ammonia, methylamine, dimethyl amine, ethylamine, diethylamide, (different) propyl group amine, two (different) propyl group amine, monoethanolamine, N-methyl monoethanolamine, N-ehtylethanolamine, diethanolamine, trolamine, morpholine, single Propanolamine, dipropanolamine, tripropanol amine, 2-amino-2-methyl-1, ammediol, amino ethyl ethanolamine and N, N, N ', N '-four (2-hydroxypropyl) quadrol.
In above-mentioned general formula (XII), m is 1 or bigger number, and is preferred 1 to 300, more preferably 1 to 200, further preferred 5 to 100.
Mentioned component (E2) can comprise and contain one or more unitary polymkeric substance, and described unit is for example by phenol or have substituent phenol and unit that the alkylene oxide adducts matter of formaldehyde dehydrogenative condensation product (N1) constitutes; Unit by compound (N2) formation that forms by epoxy alkane chain end and alkyl etherificate with compound (N1); Unit by compound (N3) formation that forms by the epoxy alkane chain end that replaces above-claimed cpd (N1) with the alkyl that contains isocyanate group or ester group; Unit by compound (N4) formation that forms by the group (for example sulfonate group, sulfate group, phosphate group and carboxylic acid ester groups) of introducing anionic hydrophilic at the epoxy alkane chain end of above-claimed cpd (N1).
When above-claimed cpd (N1) forms, can use together can with phenol or compound, for example Resorcinol, catechol, Resorcinol, methyl-phenoxide etc. with substituent phenol cocondensation.
Therefore, can be used as mentioned component (E2) by the polymkeric substance that one or more above-claimed cpds (N1) to (N4) reaction is obtained.
In addition, when forming above-claimed cpd (N1), phenol or have substituent phenol and epoxy alkane etc. for example oxyethane, propylene oxide, butylene oxide ring, tetrahydrofuran (THF) (1, the 4-butylene oxide ring), long-chain alpha-olefin oxide compound and styrene oxide carry out addition polymerization.(R when expression in above-mentioned general formula (XII)
5-O)
mWhen the addition polymerization of part by epoxy alkane etc. forms, (R
5-O) kind depends on the kind of epoxy alkane of being added into etc.The polymerized form of the epoxy alkane that adds etc. is not limited especially, can be random copolymerization, block copolymerization or the random/block copolymerization of the homopolymerization of a kind of epoxy alkane etc., two or more epoxy alkane etc.As (R
5-O)
mWhen part is polyalkylene oxide, R
5The alkylidene group that preferably has 2 to 4 carbon atoms, preferred especially ethylidene.As (R
5-O)
mWhen the copolymerization of part by two or more epoxy alkane etc. formed, a kind of in the preferred epoxy alkane was oxyethane.In this case, m is preferably 1 to 300, and more preferably 1 to 200, further preferred 5 to 100.
Above-claimed cpd (N4) can be according to the method for routine, the compound of the anionic hydrophilic group by will having above-mentioned example explanation and some or all terminal portionss (being generally hydroxyl) reaction acquisition of compound (N1).
As mentioned component (E2), can use commercially available product, " ADECANOL AS-113 " (trade(brand)name) that for example can use ADEKA company to produce.
Can use independent one or both or the multiple combination of mentioned component (E2).
When having only composition (E2) as composition (E), the total amount of supposing composition (A), composition (B) and composition (C) is 100 quality %, preferred 0.01 to the 30 quality % of the content of composition (E) in anti-static resin composition of the present invention, more preferably 0.1 to 30 quality %, further preferred 1 to 25 quality %, preferred especially 3 to 20 quality %.When the content of composition (E2) is excessive, the appearance poor of moulded product sometimes, when content was too low, sometimes antistatic to improve effect not enough.
Contain unitary boron compound (E3) (being also referred to as " composition (E3) " in the present invention) by above-mentioned general formula (XIII) expression for preferably containing described unit content 90 to 100 quality %, more preferably 95 to 100 quality %, the further compound of preferred 98 to 100 quality %.
Preferred component (E3) is for containing the polymer compound of at least 5 or more a plurality of said units.
The unitary compound that preferably contains by above-mentioned general formula (XIII) expression is the polymerization charge transfer type conjugate by following general formula (XIV) expression, it is semi-polarity organo-boron polymer compound and one or both or multiplely has hydroxyl and reaction product that add up to the tertiary amine of 5 to 82 carbon atoms that reaction ratio is that a basic nitrogen atom is to a boron atom.
Wherein q is 0 or 1; When q=1, T is-(T
1)
s-(T
2)
t(T
3)
u-(T wherein
1And T
3, can be for differing from one another or identical, for having a terminal ether residue and adding up to the oxygen-containing hydrocarbon base of 100 or still less carbon atom; T
2Group for following formula:
(R wherein
9For having the alkyl of 1 to 82 carbon atom) or the group of following formula:
(R wherein
10For having the alkyl of 2 to 13 carbon atoms),
And s, t and u are respectively 0 or 1);
R
6, R
7And R
8Can be that differ from one another or identical organic group, r is 10 to 1000.
R in above-mentioned general formula (XIV)
6, R
7And R
8Comprise for example alkyl, alkoxyl group, phenoxy group, benzyloxy and aklylene glycol group.These groups for example can have, and the such functional group of hydroxyl maybe can have substituting group.
Above-mentioned charge transfer type conjugate comprises the conjugate by following chemical formula (XV) to (XXII) expression.In each following chemical formula, hydrogen atom or hydroxyl are incorporated on each end carbon and the Sauerstoffatom usually.
(wherein R ' is 20 polybutene residue for having mean polymerisation degree.)
Above-mentioned polymerizability charge transfer type conjugate can be by at Japanese Patent No.2, the method preparation of describing in 573,986.
In addition, can use commercially available product as composition (E3), for example " HIGHBORON 400N " (trade(brand)name) of production such as BoronInternational company is suitable.
In preparation of compositions, mentioned component (E3) can be mixed separately or as mixed with the mixture (composition) of mentioned component (A), composition (B), composition (C) etc.The latter's example comprises " HIGHBORON MB400N-8LDPE " (trade(brand)name) that Boron International company produces, and it is for using the masterbatch of polyethylene as matrix.
Can use a kind of separately of mentioned component (E3), or two or more combination.
When only using composition (E3) as composition (E), the total amount of supposing composition (A), composition (B) and composition (C) is 100 quality %, preferred 0.01 to the 30 quality % of the content of composition (E3) in anti-static resin composition of the present invention, more preferably 0.05 to 20 quality %, further preferred 0.1 to 10 quality %, preferred especially 0.3 to 5 quality %.When composition (E3) when content is excessive, the appearance poor of moulded product sometimes, when its content was too low, sometimes antistatic to improve effect not enough.
Nonionogenic tenside mentioned above (E4) (being also referred to as " composition (E4) " in the present invention) comprises for example ester and the nitrogenous compound of polyvalent alcohol.
The ester of polyvalent alcohol comprises for example glyceryl ester, polyglycerol esters, sorbitan ester, glycol ester and propylene glycol ester.
Glyceryl ester comprises for example glyceryl monolaurate, Tetradecanoic acid, monoester with 1,2,3-propanetriol, glycerine monopalmitate, Zerol, Glyceryl monobehenate and glyceryl monoacetate.
Polyglycerol esters comprises for example Sunsoft Q 12D, two Tetradecanoic acid, monoester with 1,2,3-propanetriols, two glycerine monopalmitates, two Zerols, two Glyceryl monobehenates and two glyceryl monooleates.
Sorbitan ester comprises for example dehydrated sorbitol mono-fatty acid ester, sorbitan list behenate, sorbitan monostearate, sorbitan list isostearate, sorbitan monolaurate and sorbitan monopalmitate.
Glycol ester comprises for example Tego-stearate.
Propylene glycol ester comprises for example propylene glycolmonostearate.
Wherein, Zerol, two Zerols, glyceryl monolaurate, Sunsoft Q 12D and sorbitan monostearate are preferred.
Nitrogenous compound comprises for example amine compound and amide compound.
Amine compound for example comprises dioxane hydramine for example dodecyl diethanolamine, tetradecyl diethanolamine, palmityl diethanolamine, octadecyldiethanol amine, oil base diethanolamine, dodecyl diisopropanolamine (DIPA), tetradecyl diisopropanolamine (DIPA), palmityl diisopropanolamine (DIPA), octadecyl diisopropanolamine (DIPA), oil base diisopropanolamine (DIPA) and N, the two hydroxyethyl alkylamines (wherein the carbonatoms on alkyl is generally 12 to 22) of N-.
Amide compound comprises for example dodecyl diglycollic amide, tetradecyl diglycollic amide, palmityl diglycollic amide, docosyl diglycollic amide, oil base diglycollic amide, dodecyl diisopropanol acid amides, tetradecyl diisopropanol acid amides, palmityl diisopropanol acid amides, octadecyl diisopropanol acid amides and oil base diisopropanol acid amides.
Wherein, amine compound is preferred, and dodecyl diethanolamine and octadecyldiethanol amine are particularly preferred.
In preparation of compositions, mentioned component (E4) can be mixed separately, or as mixing with the mixture (composition) of mentioned component (A), composition (B), composition (C) etc.Under latter instance, can improve the miscibility in composition.
Can use a kind of separately of mentioned component (E4), or two or more combination.
When having only composition (E4) as composition (E), the total amount of supposing composition (A), composition (B) and composition (C) is 100 quality %, the content of composition in anti-static resin composition of the present invention (E4) is preferably 0.01 to 30 quality %, more preferably 0.05 to 20 quality %, further preferred 0.1 to 10 quality %, preferred especially 0.5 to 5 quality %.When the content of composition (E4) is excessive, the appearance poor of moulded product sometimes, when content was too low, sometimes antistatic to improve effect not enough.
When using mentioned component (E4), in order further to improve the anti-static function that obtains from composition (E4), it can mix with the more higher alcohols with 12 to 18 carbon atoms, lubricant, silica gel, Calucium Silicate powder etc.Perhaps, those compositions of making masterbatch can be used to improve blended purpose.As such prescription, preferably use those to contain the prescription of 20 quality % or more composition (E4).
Compound as composition of the present invention (E4) is commercially available acquisition, comprises ELECTROSTRIPPER TS-5, EA, TS-3B, TS-2B, TS-13B, TS-7B (trade(brand)name) that KaoCorporation produces.
As mentioned above, as composition (E), can be used in combination two or more that are selected from mentioned component (E1), composition (E2), composition (E3) and composition (E4).The combination of preferred especially mentioned component (E1) and composition (E4).When two or more are selected from mentioned component (E1), composition (E2), composition (E3) and composition (E4) when being used in combination, the total amount of supposing composition (A), composition (B) and composition (C) is 100 mass parts, preferred 0.01 to 30 mass parts of its total amount, more preferably 0.01 to 15 mass parts, further preferred 0.1 to 10 mass parts and preferred especially 0.5 to 7 mass parts.When composition (E) when content is excessive, the appearance poor of moulded product sometimes, when content was too low, sometimes antistatic to improve effect not enough.
According to purpose and purposes, anti-static resin composition of the present invention can further mix with additive, and described additive for example static resistance is given auxiliary agent, processing aid, filler, antioxidant, thermo-stabilizer, softening agent, filler, UV absorption agent, anti-erosion agent, light stabilizer, static inhibitor, fire retardant, lubricant, antiseize paste, tinting material, whipping agent, antiseptic-germicide and crystal nucleation additive.
In the present invention, preferably contain the anti-static function that antistatic imparting agent obtains from composition (B) with further improvement.Can use static resistance to give a kind of separately of auxiliary agent, or two or more combination.
Static resistance is given auxiliary agent and is for example comprised for example salt of lithium, sodium and potassium of basic metal; With the alkaline-earth metal salt of magnesium and calcium for example.
The kind of salt comprises for example inorganic acid salt, for example halides hydrochlorate (halides), vitriol and perchlorate; With organic acid salt for example carboxylate salt, dicarboxylate, alkylsulfonate, fragrant sulfonate (comprising alkylbenzene sulfonate) and fluorinated sulfonate.
Halogenide comprises for example lithium chloride, sodium-chlor, Repone K, lithiumbromide, Sodium Bromide and Potassium Bromide.
Perchlorate comprises for example lithium perchlorate, sodium perchlorate and potassium perchlorate.
Carboxylate salt comprises for example potassium acetate and lithium stearate.
Alkylsulfonate preferably has the salt of salt, for example octyl group sulfonic acid, dodecyl sodium sulfonate, tetradecyl sulfonic acid, octadecyl sulfonic acid, tetracosyl sulfonic acid and the 2-ethylhexyl sulfonic acid of the alkylsulphonic acid of 8 to 24 carbon atoms.
Fragrant sulfonate preferably has the salt of the aromatic sulphonic acid of 6 to 18 carbon atoms, for example the salt of phenylbenzimidazole sulfonic acid, naphthyl sulfonic acid, octyl phenyl sulfonic acid, dodecylphenyl sulfonic acid, dibutyl phenylbenzimidazole sulfonic acid, dinonyl phenylbenzimidazole sulfonic acid, dimethyl naphthyl sulfonic acid, di-isopropyl naphthyl sulfonic acid and dibutyl naphthyl sulfonic acid.
Static resistance is given auxiliary agent and can be mixed during anti-static resin composition of the present invention preparation, can be mixed at any time, for example, before composition (B) polymerization, between composition (B) polymerization period or after composition (B) polymerization.
Static resistance is given the combined amount of auxiliary agent, and the amount of supposing composition (B) is 100 mass parts, preferred 0.001 to 10 mass parts, further preferred 0.01 to 5 mass parts.
As long as transparency and anti-static function be variation not, processing aid is not limited especially.Its example comprises acrylate copolymer, styrene polymer and fluorinated polymer, its every kind those (weight-average molecular weight is 1,000,000 or more) that all preferably have ultra-high molecular weight.They can use separately or two or more being used in combination.
Preferred 0.1 to 10 mass parts of the combined amount of processing aid supposes that the total amount of composition (A), composition (B) and composition (C) is 100 mass parts.Within this scope, can improve the consistency of composition (A), composition (B) and composition (C), can improve the extrusion moulding ability of anti-static resin composition.
According to purpose, purposes etc., as filler, can be with for example, powdered, (comprising whisker) form blocky, hollow, flat or fiber are used by metal, alloy, mineral compound, organic compound, polymer compound, inorganic/organic those materials of constituting such as composition.These fillers can use separately or two or more being used in combination.
Filler comprises for example glass fibre, sheet glass, the fiber of milling of glass fibre, granulated glass sphere, Hollow Glass Sphere, carbon fiber, the fiber of milling of carbon fiber, aromatic polyamide fibre, phenolic resin fibre, trevira, ZnOw, potassium titanate crystal whisker, aluminium borate whisker, aluminum oxide, silicon-dioxide, talcum, lime carbonate, wollastonite, mica, kaolin, montmorillonite, hectorite, organically-modified montmorillonite, tin dressing titanium oxide, the silicon-dioxide of tin dressing, the carbon fiber of nickel dressing, silver, copper, brass, iron and carbon black.These can use separately or two or more are used in combination.
For improving the dispersiveness of filler, can use the filler of having handled with conventional coupler, surface treatment agent, filler reagent etc.Coupler comprises for example silane coupling agent, titanic acid ester coupler and aluminium coupler.
The total amount of supposing composition (A), composition (B) and composition (C) is 100 mass parts, preferred 0.1 to 200 mass parts of the combined amount of above-mentioned filler.
As tinting material, can use conventional dyestuff, pigment etc.
The total amount of supposing composition (A), composition (B) and composition (C) is 100 mass parts, preferred 0.001 to 20 mass parts of the combined amount of above-mentioned tinting material, further preferred 1 to 200 mass parts.
Anti-static resin composition of the present invention can further contain other polymkeric substance, for example thermoplastic resin, thermoplastic elastomer and thermosetting resin in order to obtain required performance as needs.
Thermoplastic resin comprises for example polyamide resin; Vibrin is poly terephthalic acid Aden ester, polyethylene terephthalate, polyarylester and liquid crystal polyester for example; Polyphenylene ether; Polyphenylene sulfide; Aromatic polycarbonate; Thermoplastic polyurethane; Phenoxy resin; The multipolymer of the multipolymer of PMMA resin, ABS resin, ASA resin, AES resin, HIPS, AS resin, PS resin, MS resin, methyl methacrylate and maleimide compounds and vinylbenzene and maleimide compounds.Thermoplastic elastomer comprises for example polyamide elastomer and polyester elastomer.
And thermosetting resin comprises for example Resins, epoxy, resol and urea-formaldehyde resin.
1-5. preparation method and moulded product
Anti-static resin composition of the present invention can be by putting into various forcing machines, banbury mixers, kneader, continuous kneader, roller etc. with mentioned component, additive etc., melts to mediate and obtain under heating.Every kind of composition can once add to be mediated, or the gradation adding is mediated.Just mediating the back when forming moulded product when them, can use that conventional for example injection molding of forming method, pressure forming, calendering formation, T pattern are extruded, blow molding, section bar extrusion moulding and foaming.The sheet material that obtains by aforesaid method etc. can further carry out vacuum forming etc.
Under the condition of 23 ℃ of temperature and humidity 50%RH, anti-static resin composition of the present invention and the surface resistivity preferred 5 * 10 that can obtain by the moulded product of its acquisition
12Ω or littler, more preferably 9 * 10
11Ω or littler, further preferred 9 * 10
10Ω or littler and preferred especially 5 * 10
9Ω or still less.
According to purpose, purposes etc., it is suitable that the shape of moulded product can be prepared as, and can be prepared as thin goods (5 μ m to 100mm thickness) for example sheet material and film; Rod-shaped products is pole and square rod for example; And their deformations; Plate and box etc.
When above-mentioned moulded product was sheet material, its thickness preferred 0.2 was to 10mm, and more preferably 0.5 to 5mm.
When above-mentioned moulded product is film, preferred 5 to the 200 μ m of its thickness, more preferably 10 to 150 μ m.
According to purpose and purposes, sheet material and film can have concave surface or convex surface, groove, hole etc. at its one or both sides.They can also have through hole.
Moulded product with anti-static resin composition preparation of the present invention not only is suitable for forming the simple goods of as above mentioning, but also being suitable for forming composite product, this composite product combines with pressure-sensitive adhesive film and multilayer portion sheet material that the moulded product that is made of another kind of material is for example described in the back.Therefore, when composite product when outermost has the moulding section that anti-static resin composition of the present invention constitutes, it can keep above-mentioned surface resistivity under these conditions, and is good especially on anti-static function.In addition, when other material mentioned above had the transparency, the transparency of whole composite product was good.
2. antistatic/pressure-sensitive-adhesive resin composition
Antistatic/pressure-sensitive-adhesive resin composition of the present invention is characterized in that comprising: the polyolefin resin of 0 to 59 quality % mentioned component (A) (except that following ingredients (B)), the segmented copolymer of 3 to 60 quality % mentioned components (B); Polymkeric substance and/or its hydrogenated products (prerequisite is the 100 quality % that add up to of mentioned component (A), composition (B) and composition (C)) with 35 to 97 quality % mentioned components (C).For composition (A), composition (B) and composition (C), be suitable for about the foregoing description of anti-static resin composition of the present invention for each composition.
According to first embodiment preferred of antistatic/pressure-sensitive-adhesive resin composition of the present invention, mentioned component (A), composition (B) and composition (C) content are respectively 0 to 40 quality %, 6 to 25 quality % and 35 to 94 quality %, preferred 0 to 35 quality %, 8 to 20 quality % and 45 to 92 quality %, more preferably 0 to 30 quality %, 8 to 18 quality % and 52 to 92 quality % and further preferred 0 to 25 quality %, 8 to 16 quality % and 59 to 92 quality %.By the kind and the content of selection component (C), can control viscosity with other member.That is, the content of the vinyl bonds that contains in the above-mentioned polymer blocks (c1) at constituent (C) is preferably 60-90%, more preferably during 70-85%, can demonstrate good viscosity.As composition (C), " DYNARON 1320P ", " DYNARON 1321P " (trade(brand)name) of preferably using JSR Corporation to produce.In addition, the hydrogenated products that contains the polymkeric substance of polymer blocks (c1) by suitable mixing helps viscosity controller, and the vinyl bonds content of described polymer blocks (C1) is less than 60% part as composition (C).
When mentioned component (A) when content is excessive, sometimes viscosity is not enough.
When mentioned component (B) when content is excessive, the degraded appearance of moulded product sometimes.When its content is too low, the anti-static function variation.
When mentioned component (C) when content is excessive, anti-static function variation sometimes.When its content was too low, sometimes viscosity was not enough.
Can be suitable on the support film that constitutes by polyolefin resin, forming transparent bonding coat according to the antistatic/pressure-sensitive-adhesive resin composition of above-mentioned first preferred embodiment and obtain transparent film.
Second of antistatic/pressure-sensitive-adhesive resin composition preferred embodiment according to the present invention, the antistatic/pressure-sensitive-adhesive resin composition that provides is made of the mentioned component (A) of 0 to 59 quality %, the mentioned component (B) of 3 to 60 quality % and the mentioned component (C) of 40 to 97 quality %, wherein mentioned component (A) comprises polyolefine (A '-1) and/or by the polyolefine of functional group modification (A '-2), and mentioned component (C) is the hydrogenated products of the polymkeric substance that mainly is made of conjugated diene compound unit and aromatic ethenyl compound unit.
Can be suitable on support film, forming transparent bonding coat obtaining transparent film according to the antistatic/pressure-sensitive-adhesive resin composition of second embodiment preferred, described support film by various polymkeric substance for example styrene resin constitute.
Comprise polyolefin resin (A '-1) and/or by the polyolefin resin of functional group modification (A '-2) according to the composition in the antistatic/pressure-sensitive-adhesive resin composition of second embodiment preferred (A).
Polyolefin resin (A '-1) is not for there being the polyolefin resin of modification, and all descriptions of above-mentioned polyolefin resin about anti-static resin composition of the present invention (A) are applicable to this.Polyolefin resin (A '-1) is preferably and contains at least a alkene with 2 to 10 carbon atoms as the polymkeric substance that constitutes monomeric unit, the preferred especially polymkeric substance that mainly is made of ethene.
In antistatic/pressure-sensitive-adhesive resin composition according to second embodiment preferred, the polyolefin resin of Shi Yonging (A '-1) has enough molecular weight to be used for moulding resin at normal temperatures herein, for example, when ethene is main component, it have with measure according to JISK6922 preferred 0.01 to 100g/10min, the more preferably corresponding molecular weight of 0.03 to 70g/10min melt flow rate (MFR).Polyethylene as using in addition can use any high density polyethylene(HDPE), new LDPE (film grade) and linear low density polyethylene.
Mentioned component (A '-2) is by the polyolefin resin of functional group modification.Polyolefin resin optimization polypropylene and polyethylene, more preferably low-molecular-weight polypropylene, low molecular weight polyethylene, preferred especially low molecular weight polyethylene.The weight-average molecular weight of above-mentioned low-molecular-weight polyolefin preferred 1,000 to 100,000, further preferred 5,000 to 60,000 and preferred especially 8,000 to 50,000.Low-molecular-weight polyolefin can obtain by the heating degradation method of polymerization process or high molecular polyolefine.From the viewpoint of functional group modification easiness, preferably those are by resins of heating degradation method acquisition.Can obtain low-molecular-weight polyolefin by the heating degradation method, for example by in rare gas element usually at 300 ℃ to 450C heating-degraded macromolecular weight polyolefin 0.5 to 10 hour (for example method of in Japanese kokai publication hei 3-62804, describing).
Comprised following method by functional group modification, promptly add unsaturated acid, unsaturated acid anhydride, contain epoxide group unsaturated compound, contain hydroxyl unsaturated compound, contain unsaturated compound that the oxazoline group is arranged, contain amino unsaturated compound, contain the unsaturated compound etc. of the amino of replacement.Be preferably unsaturated acid and unsaturated acid anhydride.
The unsaturated acid of Shi Yonging comprises for example vinylformic acid, methacrylic acid, Ba Dousuan, styracin, methylene-succinic acid and toxilic acid herein, and these acid can use separately or two or more are used in combination.Unsaturated acid anhydride comprises for example maleic anhydride, itaconic anhydride, chlorine itaconic anhydride, chlorine maleic anhydride and citraconic anhydride, and these acid anhydrides can use separately or two or more are used in combination.Maleic anhydride preferably.
The amount of supposing polyolefin resin is 100 quality %, and the above-mentioned content of unsaturated compound in mentioned component (A '-2) that contains functional group is preferably 0.5 to 25 quality %, further preferred 1 to 20 quality % and preferred especially 1 to 15 quality %.Use contains following the carrying out of above-mentioned modifying method of the unsaturated compound of functional group, for example according to solution methods, melting method or other method, by the modified polyolefin resin of choosing wantonly with the unsaturated compound that contains functional group in the presence of the organo-peroxide that has.
In the commercially available acquisition of material of mentioned component (A '-2) scope, the YUMEX 1001,1003,1010,100TS, 110TS, 2000, the CA60 (trade(brand)name) that produce of Sanyo chemistry company limited for example.
Mentioned component (A '-1) is used to control pressure sensitive adhesive viscosity.On the other hand, when preparation during pressure-sensitive adhesive film, mentioned component (A '-2) is used to improve binding property between tackiness agent and the supporter or the former and coats binding property between the priming paint of supporter.
In antistatic/pressure-sensitive-adhesive resin composition according to second embodiment preferred, total amount with respect to composition (A), composition (B) and composition (C) is 100 quality %, the scope of mentioned component (A) amount of using is 0 to 59wt%, preferred 1 to 59 quality %, further preferred 1 to 48 quality %, further more preferably 2 to 45 quality %, preferred especially 3 to 40 quality %.Total amount with respect to composition (A), composition (B) and composition (C) is 100 quality %, both preferred amounts of being used to strengthen mentioned component (A '-2) effect of mentioned component (A '-1) and composition (A '-2) all are 2 to 37 quality %, further preferred 2 to 35 quality %, preferred especially 5 to 30 quality %.When mentioned component (A '-1) during less than the scope as above mentioned, the control of viscosity is poor; When it surpasses this scope, differences in viscosity.On the other hand, when mentioned component (A '-2) during less than the scope as above mentioned, the binding property between tackiness agent and the supporter or the former and the binding property that is coated in the pressure sensitive adhesion membrane prepare between the priming paint on the supporter are not fully improved; When surpassing this scope, viscosity trends towards variation.
Composition (B) is a segmented copolymer, it comprises olefin polymer block and hydrophilic polymer block, in the antistatic/pressure-sensitive-adhesive resin composition according to second embodiment preferred, above the description about anti-static resin composition of the present invention goes for this.
In antistatic/pressure-sensitive-adhesive resin composition according to second embodiment preferred, when not containing composition (A), total amount with respect to composition (B) and composition (C) is 100 quality %, the amount that mentioned component (B) uses is 3 to 60 quality %, preferred 3 to 50 quality %, further preferred 5 to 40 quality %, preferred especially 5 to 35 quality %.When it during less than 3 quality %, anti-static function is poor; When it surpasses 60 quality %, the viscosity variation.When containing composition (A), total amount with respect to composition (A), composition (B) and composition (C) is 100 quality %, the amount of the composition (B) that uses is 3 to 60 quality %, preferred 3 to 59 quality %, further preferred 3 to 49 quality %, further more preferably 5 to 48 quality %, preferred especially 5 to 42 quality %.When it during less than 3 quality %, anti-static function is poor; When it surpasses 59 quality %, the viscosity variation.
In the antistatic/pressure-sensitive-adhesive resin composition of second embodiment preferred according to the present invention, composition (C) is the hydrogenated products of the polymkeric substance that mainly is made of conjugated diene compound unit and aromatic ethenyl compound unit, and above the description about anti-static resin composition of the present invention goes for this.
In composition (C) according to the antistatic/pressure-sensitive-adhesive resin composition of second embodiment preferred, aromatic ethenyl compound unit and conjugated diene compound unit can constitute random copolymers, or wherein each forms the segmented copolymer of block separately, and further they can form wherein that random copolymers and segmented copolymer are the blended mixed forms.Preferred component (C) is the hydrogenation product of the segmented copolymer that comprises mainly the polymer blocks (c1) that is made of the conjugated diene compound unit and the main polymer blocks (c2) that is made of the aromatic ethenyl compound unit.
When the antistatic/pressure-sensitive-adhesive resin composition according to second preferred embodiment is used as the pressure sensitive adhesive of display element protective membrane; from the easiness of control bond strength and the easiness viewpoint of acquisition pressure sensitive adhesive transparency, the structure of mentioned component (C) is preferably said structure (VII) especially.
In composition (C) according to the antistatic/pressure-sensitive-adhesive resin composition of second embodiment preferred, the ratio optimization aromatic vinyl compound/conjugated diene compound of aromatic ethenyl compound and conjugated diene compound=5-70/30-95 quality %, further preferred 10-65/35-90 quality % and preferred especially 15-60/40-85 quality %.
In the hydrogenated products of conduct according to the composition (C) of the antistatic/pressure-sensitive-adhesive resin composition of second embodiment preferred, the carbon-to-carbon double bond to small part in the conjugated diene compound mainly is hydrogenated.In other words, the hydrogenation product is used as composition (C), the carbon-to-carbon double bond of the conjugated diolefine part of the multipolymer of wherein as above mentioning is by partly or entirely hydrogenation, and preferred hydrogenation ratio is 10 to 100%, and further preferred 50 to 100% and preferred especially 90 to 100%.
In antistatic/pressure-sensitive-adhesive resin composition according to second embodiment preferred, when not containing composition (A), total amount with respect to composition (B) and composition (C) is 100 quality %, the usage quantity of mentioned component (C) is 40 to 97 quality %, preferred 50 to 97 quality %, further preferred 60 to 95 quality %, preferred especially 65 to 95 quality %.When it is less than 40 quality %, the viscosity variation; When it surpassed 97 quality %, anti-static function was poor.When containing composition (A), total amount with respect to composition (A), composition (B) and composition (C) is 100 quality %, and the usage quantity of composition (C) is 40 to 97 quality %, preferred 50 to 97 quality %, further preferred 50 to 93 quality %, preferred especially 55 to 92 quality %.When it is less than 40 quality %, the viscosity variation; When it surpassed 97 quality %, anti-static function was poor.
Can be further mix with composition (E), various additive, other polymkeric substance etc. according to the antistatic/pressure-sensitive-adhesive resin composition of first and second embodiment, described composition (E) can mix with the anti-static resin composition of the invention described above.For the kind and the content of these materials, above the description about anti-static resin composition of the present invention goes for this.
Antistatic/pressure-sensitive-adhesive resin composition of the present invention can heat down fusing and mediates and obtain by mentioned component (A), composition (B), composition (C), additive or the like being put into various forcing machines, banbury mixers, kneader, continuous kneader, roller etc.Every kind of composition can once all add kneading, or separately adds kneading.Just mediating the back when forming moulded product when them, can use that conventional for example injection molding of forming method, pressure forming, calendering formation, T mould are extruded, blow molding, template are extruded, section bar extrusion moulding and send out the foam moulding.The sheet material that obtains by aforesaid method etc. can be further through vacuum forming etc.
Under 23 ℃ of temperature and humidity 50%RH condition, the surface resistivity preferred 5 * 10 that antistatic/pressure-sensitive-adhesive resin composition of the present invention and the moulded product that is obtained by it can reach
12Ω or littler, more preferably 9 * 10
11Ω or littler, further preferred 9 * 10
10Ω or littler, preferred especially 5 * 10
9Ω or littler.
Suitable shape can be prepared as according to moulded products such as purpose, purposes, thin goods for example sheet material and film can be prepared as; The handful that rod-shaped products is for example round and the handful of side; In addition and their deformations etc.
When above-mentioned moulded product was sheet material, its thickness preferred 0.2 was to 10mm, and more preferably 0.5 to 5mm.
When above-mentioned moulded product was film, its thickness was preferably 5 to 200 μ m, more preferably 10 to 150 μ m.
According to purpose and purposes, can have concave surface or convex surface, groove, hole etc. at the one or both sides of sheet material and film.They can also have through hole.
Moulded product by antistatic/pressure-sensitive-adhesive resin composition preparation of the present invention also is appropriate to form compound artifact, described compound artifact and the moulded product example that is made of other material multi-layer sheet combination as described later.Therefore, when compound artifact when outermost has the moulding section that is made of antistatic/pressure-sensitive-adhesive resin composition of the present invention, its above-mentioned surface resistivity, particularly anti-static function and viscosity that can keep under these conditions is good.In addition, when other material mentioned above when being transparent, compound artifact is made the as a whole good transparency that has.
3. pressure-sensitive adhesive film
3-1. the structure of pressure-sensitive adhesive film
The antistatic/pressure-sensitive-adhesive resin composition of the invention described above can be used for forming bonding coat on the supporter that is made of various thermoplastic polymer compositions.
Therefore, according to the present invention, the pressure-sensitive adhesive film that comprises supporter and antistatic bonding coat is provided, wherein said supporter can be formed by various thermoplastic polymer compositions, antistatic bonding coat is arranged on the one side at least of described supporter, is made of the antistatic/pressure-sensitive-adhesive resin composition of as above mentioning of the present invention.
The thermoplastic polymer that can be used as the composition that forms supporter comprises elastomerics, rubber and resin in general.These can use separately or two or more are used in combination.
Elastomerics comprises for example olefin elastomer; Styrenic elastomer is styrene-butadiene-styrene block copolymer and styrene isoprene styrene block copolymer (SIS) for example; Polyester elastomer; Polyurethane elastomer; The elastomerics of vinyl chlorination thing class; The elastomerics of polyamide elastomer and Viton class.These can use separately or two or more are used in combination.
Rubber comprises for example polydiene, for example the ionomer of polyhutadiene and polyisoprene, styrene butadiene (block) multipolymer, styrene-isoprene (block) multipolymer, acrylonitrile butadiene copolymer, divinyl-(methyl) acrylate copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated butadiene polymkeric substance, ethene-alpha-olefin copolymer, ethylene-alpha-olefin-polyene copolymer, acrylic rubber, organo-silicone rubber, fluoro rubber, isoprene-isobutylene rubber and vinyl.
Above-mentioned styrene-butadiene block copolymer and above-mentioned styrene-isoprene block copolymer comprise that those have the structure of AB type, ABA type, alternation type or radial long-range block (radial teleblock) type.In addition, the hydrogenated butadiene polymkeric substance is except that the above-mentioned segmented copolymer hydrogenated products, comprise the hydrogenated products of the polymkeric substance that for example has styrene block and styrene butadiene random copolymer block, by 1,2-vinyl bonds content is 0 quality % or littler polybutadiene block and 1, and 2-vinyl bonds content is above the hydrogenated products of the polymkeric substance of the polybutadiene block formation of 20wt%.
Can use a kind of separately of above-mentioned rubber, or two or more combinations.
Thermoplastic resin comprises, polyolefin resin for example, for example polyethylene and polypropylene, acrylic resin is polymethylmethacrylate for example, styrene resin is polystyrene and rubber-reinforced styrene resin for example, vibrin is polyethylene terephthalate and polybutylene terephthalate for example, and polyamide resin is nylon 6, nylon 66 and nylon 46 for example, polycarbonate resin, fluoride resin, polysulfones, polyphenylene sulfide and liquid crystalline polymers.These materials can use separately or two or more are used in combination.In these resins, polyolefin resin, acrylic resin, styrene resin, vibrin, polyamide resin and polycarbonate resin are preferred, and polyolefin resin and styrene resin are particularly preferred.
Contain polyolefin resin as long as can be used as the polyolefin resin composition of supporter formed material, it can be separately a polyolefin resin, maybe can just not be limited especially for the mixture of polyolefin resin and other composition (for example additive and other polymkeric substance).Under latter instance, anti-static resin composition of the present invention can directly use, and maybe can use other composition.When requiring anti-static function, preferred especially use anti-static resin composition of the present invention.
The said polyolefins resin is the homopolymer with alkene of two or more carbon atoms, the multipolymer of two or more alpha-olefins and the multipolymer of alpha-olefin and other vinyl monomer.Concrete example comprises for example new LDPE (film grade) (LDPE), medium-density polyethylene, high density polyethylene(HDPE) (HDPE), ultrahigh molecular weight polyethylene(UHMWPE) (UHMPE); Ethene and alpha-olefin with 3 to 12 carbon atoms be the multipolymer of propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene for example; Polypropylene (PP); Propylene and alpha-olefin with 4 to 12 carbon atoms be the multipolymer of 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene for example; Can be included in ethene-cyclic olefine copolymer and propylene-cyclic olefine copolymer in the polyolefin resin (A-1) with the anti-static resin composition blended of the invention described above; Ethylene-propylene-diene copolymer; Polymethylpentene (MPX); Ethene and vinyl monomer be the multipolymer of vinyl-acetic ester, ethyl propenoate, methacrylic acid, Jia Jibingxisuanyizhi, toxilic acid and maleic anhydride for example; With the unsaturated carboxylic acid multipolymer that obtains of vinylformic acid and the above-mentioned polyethylene of toxilic acid or derivatives thereof modification or ethene and alpha-olefin copolymer for example.In addition, can use the mentioned component (B) that in anti-static resin composition of the present invention, comprises.These can be used alone or two or more are used in combination.
Therefore, can only use the mentioned component (A) that in anti-static resin composition of the present invention, comprises, maybe can use the combination of described composition (A) and composition (B).Under latter instance, the anti-static function of supporter is good, and the anti-static function of pressure-sensitive adhesive film is good.
Wherein, polyethylene, polypropylene, propylene-ethylene copolymers are preferred, based on all monomeric units contain propylene units 50 quality % or more polymkeric substance, be polypropylene and propylene-ethylene copolymers more preferably.Aforesaid propylene-ethylene copolymer comprises random copolymers, segmented copolymer etc., and random copolymers is particularly preferred.In addition, by these polymkeric substance and ethene-cyclic olefine copolymer or propylene-cyclic olefine copolymer of being included in the polyolefin resin (A-1) are made up, the thermotolerance of the pressure-sensitive adhesive film of preparation is good, and described polyolefin resin (A-1) may be combined in the anti-static resin composition of the invention described above.Particularly work as above-mentioned supporter by 40 quality % or more (preferred 50 quality % or more, when polyolefin resin (A-1) more preferably 60 quality % or more) forms, in 70 ℃ of temperature or higher (preferred 80 ℃ or higher, more preferably 90 ℃ or higher) temperature under, supporter do not cause any variation as the distortion and reverse.
Contain styrene resin as long as can be used as the composition of styrene resin of supporter formed material, just be not limited especially, it can be a styrene resin only, or it can be styrene resin and other mixture of ingredients (for example additive and other polymkeric substance).
Styrene resin (D) (being also referred to as " composition (D) " in the present invention) can be the monomer component resin that polymerization obtains in the presence of rubbery polymer by containing aromatic ethenyl compound, and/or can for the monomer component by will containing aromatic ethenyl compound rubbery polymer not in the presence of the resin that obtains of polymerization.Rubbery polymer comprises for example polyhutadiene, polyisoprene, styrene butadiene (block) multipolymer, styrene-isoprene (block) multipolymer, acrylonitrile butadiene copolymer, divinyl-(methyl) acrylate copolymer, hydrogenated styrene-butadiene block copolymer, the hydrogenated butadiene polymkeric substance, ethene-alpha-olefin copolymer (ethylene-propylene copolymer for example, ethylene-propylene-non-conjugated diene multipolymer, ethene-1-Butylene copolymer, ethene-butene-1 non-conjugated diene multipolymer etc.), ethylene-alpha-olefin-polyene copolymer, acrylic rubber, organo-silicone rubber, organosilicon-vinylformic acid IPN rubber and mentioned component (C) are described contains mainly the polymer blocks that is made of aromatic ethenyl compound and the segmented copolymer and the hydrogenated products thereof of the polymer blocks that mainly is made of conjugated diolefine.These materials can use separately or two or more are used in combination.Preferably polyhutadiene, butadiene-styrene copolymer and hydrogenated products thereof, ethylene-propylene copolymer, ethylene-propylene non-conjugated diene multipolymer, acrylic rubber and organo-silicone rubber.Particularly preferably be polyhutadiene and butadiene-styrene copolymer.The butadiene-styrene copolymer of Shi Yonging is used block and/or random copolymers usually herein.In styrene resin, from the support film flexible viewpoint that obtains, those materials that contain rubbery polymer are preferred.
The content of rubbery polymer in styrene resin, the amount of supposing styrene resin are 100 quality %, preferred 3 to 80 quality %, further preferred 5 to 70 quality % and preferred especially 10 to 60 quality %.
Gel content is not limited especially in the above-mentioned rubbery polymer, but when rubbery polymer be when obtaining by letex polymerization, preferred 98 quality % of gel content or still less, more preferably 40 to 98 quality %.In this scope, the film outward appearance that obtains is good.
Above-mentioned gel content can be determined by following method.That is, the 1g rubbery polymer is joined in the 100ml toluene, mixture was at room temperature left standstill 48 hours.Then mixture is filtered (this quality definition be W1 gram) by 100 order metallic screens, with the material of the toluene insoluble after filtering and metallic screen 80 ℃ of vacuum-dryings 6 hours, weigh (this quality definition is the W2 gram).By following equation (1) calculated for gel content.
Gel content (quality %)=[(W2 (g)-W1 (g))/1 (g)] * 100... (1)
During rubbery polymer preparation, the content of gel is regulated in kind by suitably setting molecular weight regulator and amount, polymerization time, polymerization temperature, polymerization conversion etc.
The aromatic ethenyl compound that is configured for the vinyl monomer of above-mentioned styrene resin comprises for example vinylbenzene, alpha-methyl styrene and hydroxy styrenes.These materials can use separately or two or more are used in combination.In these materials, vinylbenzene and alpha-methyl styrene are preferred.
Other can comprise vinyl cyanide for example, (methyl) acrylic compound, maleimide compound and various other the compound that contains functional group with the vinyl monomer of aromatic ethenyl compound copolymerization.The styrene resin that is the supporter that is used for the display element protective membrane of one of purpose of the present invention preferably has transparency; therefore the preferred vinyl monomer that uses comprises that aromatic ethenyl compound and (methyl) acrylic acid alkyl ester compound are as requisite composition; if desired; further comprise one or both or the multiple material that is selected from vinyl cyanide and maleimide compound; if further need, comprise at least a unsaturated compound that contains various other functional groups.The unsaturated compound that contains various other functional groups comprises, for example unsaturated acid compound, the unsaturated compound that contains epoxide group, replacement or do not have replacement contain amino unsaturated compound and contain the unsaturated compound that the oxazoline group is arranged.The unsaturated compound that contains various other functional groups can use separately or two or more are used in combination.
The vinyl cyanide of Shi Yonging comprises herein, for example vinyl cyanide and methacrylonitrile, and these can be used alone or two or more are used in combination.When using prussiate, can give chemical resistance.When using prussiate, be preferably 1 to 60 quality % with respect to the add-on of monomer component, more preferably 5 to 50 quality %.
(methyl) acrylic compound comprises, for example methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate and butyl methacrylate, and these compounds can use separately or two or more are used in combination.Particularly preferably be methyl methacrylate, when polyhutadiene was used as rubbery polymer, styrene/methacrylic acid methyl esters ratio can obtain the good styrene resin of transparency in the scope of 20-30/70-80 quality % (total amount 100 quality %).
Maleimide compound comprises, for example maleimide, N-phenylmaleimide and N-cyclohexyl maleimide, and these compounds can use separately or two or more are used in combination.In order to introduce the maleimide amine unit, at first maleic anhydride can be carried out imidization then by copolymerization.When using maleimide compound, can be endowed thermotolerance.When using maleimide compound, with respect to monomer component, preferred 1 to the 60 quality % of add-on, more preferably 5 to 50 quality %.
The unsaturated acid compound comprises, for example vinylformic acid, methacrylic acid, ethylacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid, Ba Dousuan and styracin, and these compounds can use separately or two or more are used in combination.
The unsaturated compound that contains epoxide group comprises for example glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether, and these compounds can use separately or two or more are used in combination.
The unsaturated compound that contains hydroxyl comprises, for example 3-hydroxyl-1-propylene, 4-hydroxyl-1-butylene, suitable-4-hydroxyl-2-butylene, anti--4-hydroxyl-2-butylene, 3-hydroxy-2-methyl-1-propylene, 2-hydroxyethyl methacrylic ester, 2-hydroxyethylmethacry,ate and N-(4-hydroxy phenyl) maleimide, these compounds can use separately or two or more are used in combination.
The unsaturated compound that contains anhydride group comprises, for example maleic anhydride, itaconic anhydride and citraconic anhydride, and these compounds can use separately or two or more are used in combination.
Containing has the unsaturated compound of oxazoline group to comprise, second alkene oxazolin for example, and these can use separately or two or more are used in combination.
The amino unsaturated compound that contains that replace or that do not have replacement comprises; for example amino-ethyl acrylate, propyl group amino-ethyl acrylate, dimethyl amino ethyl methacrylate, phenyl amino ethyl-methyl acrylate, N-vinyl diethylamide, N-ethanoyl vinyl amine, acryl amine (acrylamine), methacryloyl amine (methacrylamine), N-methacryloyl amine, acrylamide, N methacrylamide and p-aminophenyl ethene, these compounds can use separately or two or more are used in combination.
With respect to the total amount of the unsaturated compound that contains functional group that is used for styrene resin, contain preferred 0.1 to the 20 quality % of add-on and further preferred 0.1 to the 10 quality % of the unsaturated compound of various other functional groups.
Styrene resin of the present invention can be by conventional polymerization process preparation, the combination of for example letex polymerization, mass polymerization, solution polymerization, suspension polymerization and these polymerization processs.In these methods, the preferred polymerization processes that (is total to) polymkeric substance that polymerization of vinyl monomers obtains in the presence of rubbery polymer is letex polymerization and solution polymerization.On the other hand, rubbery polymer not in the presence of the preferred polymerization processes of the polymkeric substance that obtains of (being total to) polymerization of vinyl monomers be bulk polymerization, solution polymerization, suspension polymerization and letex polymerization.
When preparation is when complete, to use polymerization starter, chain transfer agents, emulsifying agent etc. by letex polymerization, these all materials can for routine known those.
Polymerization starter comprises, for example Cumene Hydroperoxide 80, to menthane hydrogen peroxide, two Cumene Hydroperoxide 80s, tetramethyl butyl hydroperoxide, tert-butyl hydroperoxide, Potassium Persulphate and Diisopropyl azodicarboxylate.
Further, cause auxiliary agent, preferably use for example various reductive agents of redox agent system, contain sugared ferric pyrophosphate prescription and sulfoxylate prescription as polymerization.
Chain transfer agents comprises, for example octyl mercaptan, n-dodecyl mercaptan, uncle's lauryl mercaptan, n-hexyl mercaptan and terpinolene.
Emulsifying agent comprises, for example alkylbenzene sulfonate Sodium dodecylbenzene sulfonate, aliphatic sulfonate sodium lauryl sulphate, higher fatty acid salt potassium laurate, potassium stearate, potassium oleate and potassium palmitate and sylvate potassium rosinate for example for example for example for example.
About the use-pattern of rubbery polymer in letex polymerization and vinyl monomer, can in the presence of whole rubbery polymers, all add vinyl monomer and carry out, or can add and polymerization in batches or continuously in polymerization.In addition, can in polymerization process, add the part rubbery polymer.
After letex polymerization, the latex of acquisition condenses with condensing agent usually, washes with water then, and drying obtains the styrene resin powder.At this moment, two or more suitably can be mixed by the latex that letex polymerization obtains, condense then.The example of the condensing agent of Shi Yonging comprises for example for example sulfuric acid, hydrochloric acid, acetate, citric acid and oxysuccinic acid of calcium chloride, sal epsom and magnesium chloride and acid of inorganic salt herein.
When styrene resin during by solution polymerization operable solvent be the inertia polymer solvent, it is generally used for radical polymerization.Its example comprises aromatic hydrocarbon, for example ethylbenzene and toluene, and ketone is methyl ethyl ketone and acetone for example, acetonitrile, dimethyl formamide, N-Methyl pyrrolidone etc.
Polymerization temperature is preferably 80 to 140 ℃ of scopes, more preferably 85 to 120 ℃ of scopes.In the polymerization process, can use polymerization starter, or polymerization can be undertaken and not use polymerization starter by thermopolymerization.The preferred polymerization starter that uses for example comprise ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxyester, hydrogen peroxide, Diisopropyl azodicarboxylate, benzoyl peroxide and 1,1 '-azo two (hexanaphthene-1-nitrile).
In addition, when using chain transfer agents, it can be for example mercaptan, terpinolene and α-Jia Jibenyixierjuwu.
When being prepared, can use the polymerization starter in about solution polymerization, described, chain transfer agents etc. by mass polymerization or suspension polymerization.
The amount of residual monomer is preferred 10 in the styrene resin that is obtained by above-mentioned polymerization process, and 000ppm or still less is further preferred 5,000ppm or still less.
By the styrene resin that obtains at polymerization of vinyl monomers in the presence of the rubbery polymer contain usually vinyl monomer by graft copolymerization to the rubbery polymer multipolymer and be not grafted to not grafting composition ((being total to) polymkeric substance of above-mentioned vinyl monomer) on the rubbery polymer.
Preferred 20 to the 200 quality % of percentage of grafting of the styrene resin that obtains by polymerization of vinyl monomers in the presence of rubbery polymer, further preferred 30 to 150 quality % and preferred especially 40 to 120 quality %, percentage of grafting can pass through following equation (2) and determine.
Percentage of grafting (quality %)=((T-S)/S) * 100 (2)
In aforesaid equation (2), the 1g styrene resin of T for obtaining by the polymerization that in 20ml acetone, is added in the presence of the rubbery polymer by vinyl monomer, vibrate mixture 2 hours by vibrator, pass through the whizzer centrifugal mixture then (in speed of rotation 23,000rpm) separated soluble material and insoluble material in 60 minutes and the quality (g) of the insoluble material that obtains, S is the quality (g) of the rubbery polymer that contains in 1g composition (D).
Limiting viscosity [η] (using methyl ethyl ketones to measure as solvent at 30 ℃) about composition soluble material in acetone of styrene resin of the present invention is preferably 0.2 to 1.2dl/g, and further preferred 0.2 to 1.0dl/g and preferred especially 0.3 to 0.8dl/g.
Polymerization of vinyl monomers in the presence of rubbery polymer and in the styrene resin that obtains dispersive graft rubber shaped polymer particulate median size be preferably 500 to 30,0000
, further preferred 1,000 to 20,000
Preferred especially 1,500 to 8,000
Can measure median size by the known method of using electron microscope.
The composition that forms supporter can only comprise thermoplastic polymer, or also can comprise static inhibitor.The add-on of static inhibitor, the total amount of supposing thermoplastic polymer and static inhibitor is 100 quality %, is 3 to 30 quality %, preferred 5 to 25 quality %, further preferred 8 to 20 quality % and preferred especially 10 to 20 quality %.When add-on during, can not obtain required anti-static function less than 3 quality %.When it surpasses 30 quality %, can not obtain uniform film.
Static inhibitor is not limited especially.Can use known static inhibitor.Preferred static inhibitor can not damage the static inhibitor of transparency owing to its adding for those.Preferred static inhibitor comprise mentioned component (B) for example and hereinafter shown in static inhibitor (F), static inhibitor (F) comprises the segmented copolymer by polyamide-block (F-2-1) and hydrophilic polymer block (F-2-2) formation.Static inhibitor shown in particularly preferably being hereinafter (F).
Static inhibitor (F) is made of polyamide-block (F-2-1) and hydrophilic polymer block (F-2-2).The polymeric amide of Shi Yonging for example comprises the polymeric amide derived from diamines and dicarboxylic acid composition herein, described two amine components for example are aliphatic, alicyclic or aromatic diamines, quadrol for example, tetramethylene-diamine, hexamethylene-diamine, decamethylene diamine (decamethylenediamine), 2,3,4-or 2,4,4-trimethylene hexamethylene-diamine, 1,3-or 1, two (amino methyl) hexanaphthenes of 4-, two (to amino hexyl) methane, phenylenediamine, m-xylene diamine, p-Xylol diamines, described diacid are and are aliphatic, alicyclic or aromatic diacid is hexanodioic acid for example, suberic acid, sebacic acid, cyclohexane cyclohexanedimethanodibasic, terephthalic acid and m-phthalic acid; By the lactan polymeric amide that obtains of the ring-opening polymerization of hexanolactam and lauryl lactam for example; Derived from aminocarboxylic acid for example omega-amino-caproic acid, omega-amino-enanthic acid, amino undecanoic acid and 1, the polymeric amide of the amino dodecylic acid of 2-; With the polymeric amide of the copolymerization of these materials and the blended polymeric amide of these materials.
As the hydrophilic polymer block (F-2-2) that uses, can use above-mentioned those that describe about hydrophilic polymer block (b2) herein.
The preferred polymerization processes of the static inhibitor of as above mentioning (F) is the hot melt polymerization process, and preferred concrete example is represented hereinafter.
(i) a kind of method wherein will be mixed two terminal carboxylizations that make the polymeric amide composition by the polymeric amide that polymerization obtains with di-carboxylic acid, mix with poly-(epoxy alkane) glycol then and prepare the polyethers polymeric amide with polymerization.
The method that (ii) prepares the polyethers polymeric amide, wherein in the polymerizing polyamide process, pass through to add excessive di-carboxylic acid compound, so that, adding poly-(epoxy alkane) glycol then basically by carboxylated, two ends of polymeric amide molecule obtain the polyethers polymeric amide with polymerization.
The method that (iii) prepares the polyethers polymeric amide, poly-(epoxy alkane) glycol of the composition by will preparing polymeric amide, excessive di-carboxylic acid compound and predetermined amount all add together with polymerization and obtain the polyethers polymeric amide.
In these methods, method (i) is especially preferred method.
Can also use about basic metal and/or alkaline earth salt (H) described in the explanation of above-mentioned polymer blocks (b2).
The di-carboxylic acid that is used for the molecular end of carboxylated above-mentioned polymeric amide composition comprises for example hexanodioic acid, suberic acid, sebacic acid, toxilic acid, citraconic acid, maleic anhydride, citraconic anhydride, cyclohexane dicarboxylic carboxylic acid, terephthalic acid and m-phthalic acid.The number-average molecular weight scope of above-mentioned polymeric amide of the present invention is preferred 500 to 20,000, and further preferred 500 to 10,000 and preferred especially 500 to 5,000 to realize purpose of the present invention.
Polyamide-block (F-2-1) and hydrophilic polymer block (F-2-2) quality ratio (F-2-1/F-2-2) preferable range in above-mentioned static inhibitor (F) is 90/10-10/90, further preferred 80/20-20/80 and preferred especially 70/30-30/70.
The molecular weight of above-mentioned static inhibitor (F) is not limited especially, but reducing viscosity (η
Sp/ C) (25 ℃ in formic acid solution, measure among the 0.5g/100ml) scope that reduces is preferably 1-3dl/g and more preferably 1.2 to 2.5dl/g.
And, can use a kind of separately of above-mentioned antistatic reagent (F), or two or more combination.
The PELESTAT NC6321 and the M-140 (trade(brand)name) for the production of Sanyo chemical industrial company of the commercially available acquisition of above-mentioned static inhibitor (F).
Above-mentioned thermoplastic polymer can be with its composition by acquisitions such as various forcing machines, banbury mixers, kneader, continuous kneader, rollers.
When the supporter that is made of thermoplastic polymer is used to prepare basilar membrane, see that from the viewpoint of handling film preferably has thickness 10-200 μ m.This film can be by for example calendering process, T pattern method and the blow moiding method preparation of known method, and calendering process is preferred.
Above-mentioned thermoplastic polymer can suitably contain conventional anti-erosion (anti-light) agent, antioxidant, lubricant, softening agent, tinting material, dyestuff, pore forming material, processing aid (ultra-high molecular weight acrylate copolymer, ultra high molecular weight phenylethylene polymkeric substance) etc.
3-2. the preferred embodiment of pressure-sensitive adhesive film
Under first embodiment situation of antistatic/pressure-sensitive-adhesive resin composition of the present invention, preferably use polyolefine resin composition as the thermoplastic polymer composition that constitutes supporter.From the anti-static function viewpoint of antistatic/pressure-sensitive adhesive film, preferred anti-static resin composition of the present invention is as polyolefine resin composition (first embodiment of antistatic/pressure-sensitive adhesive film).
Under second embodiment situation of antistatic/pressure-sensitive-adhesive resin composition of the present invention, preferably use styrene resin as the thermoplastic polymer composition (second embodiment of antistatic/pressure-sensitive adhesive film) that constitutes supporter.
Use the antistatic/pressure-sensitive adhesive film of the antistatic/pressure-sensitive-adhesive resin composition of first embodiment of the present invention to comprise:
Embodiment [i] wherein film comprises supporter (hereinafter being referred to as " supporter (1) ") and the antistatic bonding coat that is made of separately composition (A);
Embodiment [ii] wherein film comprises supporter (hereinafter being referred to as " supporter (2) ") and the antistatic bonding coat that is made of anti-static resin composition of the present invention; With
Embodiment [iii] wherein film comprises supporter (hereinafter being referred to as " supporter (3) ") and the antistatic bonding coat that is made of polyolefine resin composition, and described polyolefine resin composition comprises any and non-composition (A) and composition (B) of composition (A) and composition (B).
The object lesson that constitutes the composition of the supporter (3) in the above-mentioned embodiment [iii] comprises and contains composition (A) and composition (C) but the composition that does not contain composition (B); Contain the composition that composition (B) and composition (C) still do not contain composition (A); Contain composition (A) and contain composition (B) and (C) in addition the composition of other composition; Contain composition (B) and contain composition (A) and (C) in addition the composition of other composition; Contain the composition (A) and (B) in addition the composition of other polyolefin resin.
Above-mentioned supporter (2) and (3) can contain can with anti-static resin composition blended additive of the present invention.Aspect the content of additive, above-mentioned description about anti-static resin composition of the present invention goes for this in above-mentioned supporter (2).In above-mentioned supporter (3) aspect the content of additive, except will composition (A), (B) and total amount (C) replacing with the total amount of polyolefine resin composition in anti-static resin composition of the present invention, the description of above-mentioned amount about anti-static resin composition of the present invention goes for this.
Particularly when needing anti-static function for pressure-sensitive adhesive film, anti-static resin composition of the present invention (above embodiment [ii]) is preferred.When the needs thermotolerance, preferred using ingredient (A-1) and composition (A-2) are as composition (A).
The supporter thickness of pressure-sensitive adhesive film is preferably 10 to 200 μ m, more preferably 10 to 100 μ m.
Each surface of above-mentioned supporter can have groove, concave surface or convex surface etc. on the part that antistatic/pressure-sensitive adhesive layer is set.
Preferred 1 to the 100 μ m of the thickness of antistatic/pressure-sensitive adhesive layer, more preferably 5 to 50 μ m.Above-mentioned antistatic/thickness of pressure-sensitive adhesive layer is usually less than the thickness of supporter.
Above-mentioned antistatic/pressure-sensitive adhesive layer can form or form on the two sides of supporter in the one side of supporter.Under latter instance, mean the double-sided pressure-sensitive adhesive film.It can be formed on the surperficial part or on all surfaces.
The pressure-sensitive adhesive film of above-mentioned first embodiment and second embodiment binding property between supporter and antistatic bonding coat all is good, and is good at the anti-static function on supporting body surface and antistatic bonding coat surface.
For binding property, peeling off intensity and can be preferably 300g/15mm or more under the condition among the embodiment of Miao Shuing in the back, more preferably 400g/15mm or more, further preferred 500g/15mm or more.
Anti-static function (surface resistivity under 23 ℃ of temperature and humidity 50%RH condition) in supporting body surface can be preferably 5 * 10
12Ω or littler, more preferably 9 * 10
11Ω or littler, further preferred 9 * 10
10Ω or littler and preferred especially 5 * 10
9Ω or littler.
In order to protect antistatic bonding coat, pressure-sensitive adhesive film of the present invention can have protective layer on the surface of described antistatic bonding coat.
The constitute of above-mentioned protective layer is not limited especially, but those protective layers that are made of the material that damages antistatic bonding coat when layer is peeled off hardly are preferred.Comprise polyester film particularly, for example polyethylene terephthalate (PET), polypropylene screen, styrene resin adipose membrane and polyamide membrane.
With reference to accompanying drawing pressure-sensitive adhesive film of the present invention is made an explanation.
In Fig. 1, pressure-sensitive adhesive film 1 has supporter 11 and is arranged on a lip-deep antistatic bonding coat 12 of supporter 11.
In Fig. 2, pressure-sensitive adhesive film 1 ' has supporter 11, is arranged on a lip-deep antistatic bonding coat 12 of supporter 11 and is arranged on antistatic bonding coat 12 lip-deep protective layers 13.
In Fig. 3, pressure-sensitive adhesive film 1 " have supporter 11, be arranged on two lip-deep antistatic bonding coat 12a and 12b of supporter 11 and be arranged on each lip-deep protective layer 13a and 13b of antistatic bonding coat 12a and 12b.
3-3. the preparation method of pressure-sensitive adhesive film
Pressure-sensitive adhesive film can be by conventional method preparation, and its preparation method is not limited especially.
But, in the present invention, the suitable preparation method of pressure-sensitive adhesive film is the method that comprises following steps, is about to the step of the antistatic/pressure-sensitive-adhesive resin composition coextrusion of the thermoplastic polymer composition of for example polyolefine resin composition, composition of styrene resin etc. and the invention described above.
Concrete extrusion method comprises, for example T pattern method and blow moiding method.Common every kind of composition uses under the condition of fusing, but the temperature that adds man-hour is usually based on the temperature of fusion of each composition, melt viscosity etc. and consider the shape of moulded product and thickness and selecting.
Obtaining in the step of pressure-sensitive adhesive film by coextrusion, (1) thermoplastic polymer composition and antistatic/pressure-sensitive-adhesive resin composition can be melted kneading separately earlier; (2) every kind of thermoplastic polymer composition and antistatic/pressure-sensitive-adhesive resin composition mixture of ingredients can be melted kneading when coextrusion; Can add when the coextrusion with further (3) thermoplastic polymer composition and every kind of composition of antistatic/pressure-sensitive-adhesive resin composition.And can adopt the method that above-mentioned (1), (2) and (3) method are made up.As above-mentioned thermoplastic polymer composition, can preferably use polyolefine resin composition, composition of styrene resin etc.
Mediate for the thermoplastic polymer composition fusing that will be used for supporter earlier by the preferred method that coextrusion obtains pressure-sensitive adhesive film of the present invention, by aforesaid method (2) or (3) with the antistatic/pressure-sensitive-adhesive resin composition coextrusion.
Pressure-sensitive adhesive film of the present invention not only can prepare by coextrusion, and can use following method preparation.
(1) method comprises: at first thermoplastic polymer composition is formed film by calendering process, T pattern method, blow moiding method and form supporter, choose wantonly and carry out surface treatment, extrude then and the lamination antistatic/pressure-sensitive-adhesive resin composition.
(2) method comprises: form supporter and antistatic bonding coat (film or sheet material) respectively by using thermoplastic polymer composition and antistatic/pressure-sensitive-adhesive resin composition, choose wantonly at each moulded product (preferred supporter) and want the adherent surface to carry out surface treatment, extrude mutual lamination (dry laminating material method) then.
(3) method comprises: at the compound that is coated with easy removal for example on the sheet material of silicoorganic compound (preferred polyethylene terephthalate), apply antistatic/pressure-sensitive-adhesive resin composition at the organic solvent antistatic/pressure-sensitive-adhesive resin composition that for example dissolved solution or fusing are mediated in toluene and the hexanaphthene, dry then sheet material is to obtain to have the sheet material of antistatic bonding coat.After this, this has the sheet material of antistatic bonding coat and supporter crimping so that antistatic bonding coat is transferred on the supporter, and described supporter uses polyolefine resin composition to make in addition.
Above-mentioned surface-treated concrete grammar example for example comprises, Corona discharge Treatment, flame treating, oxide treatment, Cement Composite Treated by Plasma, UV processing, ion bombardment processing and solvent treatment.These processing can be combined and carry out continuously.
And, before bonding, can form in supporting body surface and contain for example prime coat of polymine, urethane and acrylic resin of resinous principle with antistatic bonding coat.Preferred prime coat thickness is as far as possible little, preferably about 0.1 to 10 μ m, and more preferably 0.1 to 5 μ m.Described prime coat can form by apply dry then this layer of solvent (comprising water) solution with conventional method usually.
When protective layer was arranged on the antistatic bonding coat surface, it can carry out (can identical time by coextrusion) simultaneously with the formation of supporter and antistatic bonding coat, or can with reel in carry out.
4. multi-layer sheet (multilayer film)
Anti-static resin composition of the present invention is suitable for multi-layer sheet, multilayer film etc.Its embodiment comprises sheet material (or film) laminating material that for example is made of anti-static resin composition of the present invention; The two sheets (or two membranes) that sheet material (or film) that is made of anti-static resin composition of the present invention and the sheet material (or film) that is made of other material constitute; The sheet material (or film) and other material formation sheet material (or film) that are made of two-layer anti-static resin composition of the present invention sandwich its middle three-layer tablet material (or trilamellar membrane) that constitutes etc.The prime coat of mentioning in pressure-sensitive adhesive film of the present invention is described can be arranged between each layer.
The amount that contains said polyolefins resin (A-1) when anti-static resin composition of the present invention is 40 quality % or more (preferred 50 quality % or more, more preferably 60 quality % or more) time, can form multi-layer sheet (multilayer film), its 70 ℃ of temperature or higher (preferred 80 ℃ or higher, more preferably 90 ℃ or higher) down variation be difficult to take place as reversing or twisting.
As other material above, polyolefin resin, styrene resin etc. separately or the composition that contains one or more these resins be preferred.Especially, the preferred composition that only uses the composition (A) of the anti-static resin composition that constitutes the invention described above or contain it.In order for example to improve hardness, thermotolerance etc. or to give anti-static function, said composition can contain various fillers and static inhibitor etc.
In above-mentioned multi-layer sheet (multilayer film), for for example stable anti-static function of realizing, the layer thickness that is made of anti-static resin composition of the present invention is preferably 10 μ m or more, further preferred 50 μ m or more and preferred especially 80 μ m or more.
With three layers of thin slice is that example is described top composite wafer with reference to the accompanying drawings.
In Fig. 4, three-layer tablet material 2 has middle layer 22 and layer 21a and the 21b by using anti-static resin composition mentioned above to form that is made of other material.
The preparation method of above-mentioned multi-layer sheet (multilayer film) can be identical with the preparation method of pressure-sensitive adhesive film mentioned above, and coextrusion method for example T pattern method and blow moiding method is preferred.If desired, sheet material that in this way obtains and film can be further form moulded product such as plate etc. by vacuum forming etc.
5. two sides pressure-sensitive adhesive film
Antistatic/pressure-sensitive-adhesive resin composition of the present invention is suitable for the pressure-sensitive adhesive film on two sides etc.Its embodiment has the embodiment that has antistatic bonding coat on the two sides of supporter, with the same about the description of the above-mentioned pressure-sensitive adhesive film of the present invention, described antistatic bonding coat is made of the antistatic/pressure-sensitive-adhesive resin composition of the invention described above, described supporter is made of anti-static resin composition of the present invention, in addition, the embodiment that has the antistatic bonding coat that is made of above-mentioned antistatic/pressure-sensitive-adhesive resin composition on the two sides of supporter is arranged, and described supporter is made of other material.
Each supporter in these embodiments and the thickness of antistatic bonding coat can be with identical about the thickness of each supporter in the above-mentioned pressure-sensitive adhesive film description of the present invention and antistatic bonding coat.
Other material above comprises thermoplastic polymer composition except that the invention described above anti-static resin composition, for example various polyolefine resin compositions, composition of styrene resin and contain the composition of these resins.Especially, the composition that contains the composition (A) of the anti-static resin composition that formation as above mentions is preferred.In order for example to improve hardness and thermotolerance or to give anti-static function, these compositions can contain various additives.
Same with above-mentioned pressure-sensitive adhesive film of the present invention, in order to protect antistatic bonding coat etc., above-mentioned two sides pressure-sensitive adhesive film can also have protective layer on described antistatic bonding coat surface.The constituent material of this protective layer is as indicated above.
Moulded product of the present invention, promptly, the moulded product that is formed by above-mentioned anti-static resin composition is suitable at electronics and electricity field, in the OA/ household appliance technical field, in field of vehicles, in the sanitation field, at the various members of building material field etc., part etc., particularly be suitable for member that static wherein can cause significant problem, part etc.Particularly, they are used for shell, for example rly. shell, wafer shell, graticule shell and shelter shell; Pallet is liquid crystal tray, chip tray, storer pallet, CCD pallet, IC pallet for example; Carriage is the IC carrier for example; Sheet material is the protection sheet material of polarized film for example; The bobbin of sheet material or film; Film for example uses the surface protection film of display element, light guiding plate, plasma display and the polarising sheet of liquid crystal, and the protective membrane that semi-conductor is relevant is used for the protective membrane of clean room; The sheet material that is used for the clean room; Antistatic bag; Equipment is the internal part of vending machine for example.
Embodiment
Hereinafter the present invention is described in more detail by the mode of embodiment.But only otherwise leave aim of the present invention, the present invention never is limited to these embodiment.Except as otherwise noted, otherwise unit " part " and " % " both are based on quality.
1. evaluation method
In the evaluation method of various evaluations in embodiment and the comparative example as shown in hereinafter.
(1) composition (C) (styrene content of the bonding of polymkeric substance, vinyl bonds content, number-average molecular weight and hydrogenation ratio)
(1-1) styrene content of bonding
Use hydrogenation polymer determination before.By based at 699cm
-1The calibration curve that the infrared research that phenyl absorbs obtains is determined.
(1-2) number-average molecular weight
Use hydrogenation polymer determination before.Determine according to gel permeation chromatography (GPC).
(1-3) ethylenic linkage content
Use hydrogenation polymer determination before.Determine by infrared research (Morello method).
(1-4) hydrogenation ratio
Use hydrogenation polymer determination afterwards.By at 100MHz
1Unsaturated double-bond spectrum drop-out value is calculated in the H-NMR spectrum,
1H-NMR spectrum uses zellon to measure in concentration 15% as solvent.
(2) composition (D) (character of rubbery polymer, percentage of grafting and limiting viscosity)
(2-1) gel content of rubbery polymer;
Measure according to above-described method.
(2-2) number average bead diameter of rubbery polymer latex
The number average bead diameter that is used to form the rubbery polymer latex of composition (D) is passed through light scattering method measuring.Use LPA-3100 (preparation of Otsuka Electronics Co., Ltd.) as determining instrument, measure according to semi-invariant method (70 integrations).The granular size that is dispersed in the grafted rubber-like polymer particle in the composition (D) is confirmed as substantially big or small identical with latex particle with electron microscope.
(2-3) percentage of grafting of composition (D)
Measure according to above-described method.
(2-4) limiting viscosity [η] of composition (D)
Measure according to above-described method.
(3) anti-static function
(3-1) surface resistivity
With experiment slice after placing 48 hours under 23 ℃ of temperature and the humidity 50%RH condition, measure surface resistivity (Ω) with resistivity metering equipment (" HIGHRESTER-UPMCP-HT450 " (trade(brand)name) of Mitsubishi chemical company production) under the voltage 500V applying.
(3-2) anti-static function is measured;
The Static Honestmeter H-0110 that uses Shishido Electronics Co., Ltd. to produce carries out charged processing with the face as follows of pressure-sensitive adhesive film under 5kV, measure this charged fall time to 0V.
Static resistance-1; Voltage is applied to supporter (anlistatig styrene resin) face.
Static resistance-2: voltage is applied to the tackiness agent face.
(4) transparency
According to following standard evaluation.
Zero (or " transparent "); Transparency (when being placed on experiment slice on the printed matter, can seeing through experiment slice and see printed matter) is arranged.
△; Very little transparency (when being placed on experiment slice on the printed matter, can seeing through experiment slice and see indistinctly printed matter) is arranged.
*; There is not transparency; (when being placed on experiment slice on the printed matter, can not seeing through experiment slice and see printed matter).
(5) outward appearance of moulded product
The appearance on experiment slice two sides carries out visual valuation by following standard.
Zero (or " well "); Good smoothness and good appearance.
△; Some parts is poor on smoothness.
* (or " bad "); In smoothness and bad in appearance.
(6) binding property between supporter and the bonding coat
(6-1) viscosity-1
When support film with width 15mm peels off antistatic bonding coat with speed 300mm/min 90 degree, measure and peel off intensity (unit: g).
(6-2) viscosity-2
When support film with width 25mm peels off antistatic bonding coat with speed 300mm/min 180 degree, measure and peel off intensity (unit: g).
(7) binding property between antistatic bonding coat and tri acetyl cellulose (TAC) film
The TAC film of width 25mm is placed on the adhesive surface of the antistatic bonding coat of pressure-sensitive adhesive film, by the roller of mobile 2kg and its applying to and fro thereon.When peeling off angle 180 degree peel rate 300mm/min, measure afterwards and peel off intensity (unit: g).
2. the starting material of anti-static resin composition and antistatic/pressure-sensitive-adhesive resin composition
2-1. composition (A)
(1) A1 (homotype polypropylene)
" NOVATEC PP MG2T " (trade(brand)name) of using Japanese Polypro company to produce.
(2) A2 (random polypropylene)
" NOVATEC PP EG7F " (trade(brand)name) of using Japanese Polypro company to produce.
(3) A3 (using the polyethylene of metallocenes Preparation of Catalyst)
" KERNEL KF270 " (trade(brand)name) of using Japanese Polyethylene company to produce.
(4) A4 (ethylene-norbornene copolymer)
" TOPAS6013 " (trade(brand)name) of using Polyplastics company to produce.Norbornylene content be 75 to 80% and second-order transition temperature be 140 ℃.
(5) A5 (homotype polypropylene)
" NOVATEC PP FY6C " (trade(brand)name) of using Japanese Polypro company to produce.
(6) A6 (new LDPE (film grade))
" NOVATEC LL UF422 " (trade(brand)name) of using Japanese Polyethylene company to produce.
(7) A7 (new LDPE (film grade))
" Novatec LD LF122 " (trade(brand)name) of using Japanese Polyethylene company to produce.
(8) A8 (maleic anhydride modified polyethylene)
" YUMEX 2000 " (trade(brand)name) of using Sanyo chemical industrial company to produce.
(9) A9 (ethylene-norbornene copolymer)
" TOPAS8007X10 " (trade(brand)name) of using Polyplastics company to produce.Norbornylene content be 65% and second-order transition temperature be 80 ℃.
(10) A10 (vapor-phase process metallocenes types of polyethylene)
" HARMOREX NF464N " (trade(brand)name) of using Japanese Polyethylene company to produce.
2-2. composition (B)
(1) B1 (polyolefine-polyethers segmented copolymer)
" PELESTAT 230 " (trade(brand)name) of using Sanyo chemical industrial company to produce.
(2) B2 (polypropylene-polyethers segmented copolymer)
" PELESTAT 303 " (trade(brand)name) of using Sanyo chemical industrial company to produce.
2-3. composition (C)
(1) C1 (hydropolymer of high-vinyl type)
" DYNARON1321P " (trade(brand)name) of using JSR company to produce.
(2) C2 (hydropolymer) with polyethylene block
" DYNARON6200P " (trade(brand)name) of using JSR company to produce.
(3) C3 (hydropolymer of high-vinyl type)
" DYNARON1320P " (trade(brand)name) of using JSR company to produce.
(4) C4 (styrene-butadiene-styrene block copolymer)
" TR2500 " (trade(brand)name) of using JSR company to produce.
(5) C5 (hydrogenated styrene-butadiene block copolymer)
The hydrogenated styrene-butadiene block copolymer that use is obtained by preparation embodiment 1 described below.
Preparation embodiment 1
Be equipped with agitator and chuck the autoclave drying, use nitrogen replacement, put into the solution of 35 parts of hexanaphthenes and divinyl.Then, add n-Butyl Lithium, carry out the isothermal polymerization at 50 ℃.Reach at 100% o'clock at transformation efficiency,, carry out heated polymerizable at 50 ℃ to 80 ℃ to wherein adding 0.75 part of tetrahydrofuran (THF), 45 parts of divinyl and 15 parts of vinylbenzene.Reach at 100% o'clock at transformation efficiency,, further carry out polyreaction to obtain unhydrided A-B1-B2 triblock copolymer to wherein adding 5 parts of vinylbenzene.The block copolymer solution part that sampling obtains adds 0.3 part 2 in per 100 parts of segmented copolymers, and 6-two-tert-butyl catechol is afterwards by adding the heat extraction solvent.This polymkeric substance is made of 5% styrene block (A block), 60% styrene butadiene block (B1 block) and 35% butadiene block (B2 block), molecular-weight average is 200,000, wherein in the divinyl of styrene butadiene block (B1) part 1, the 2-contents of ethylene be 35% and styrene content be 15%, in the butadiene block (B2) 1, the 2-contents of ethylene is 8%.
To in hexanaphthene, react the solution that obtains by titanocene dichloride and triethyl aluminum and join in the remaining block copolymer solution, at 50 ℃ at 50kgf/cm
2Carried out hydrogenation under the hydrogen pressure 40 minutes.Add 0.3 part 2 in per 100 parts of segmented copolymers, 6-two-tert-butyl catechol removes then and desolvates to obtain block copolymer C 5.
(6) C6 (hydrogenated styrene-butadiene block copolymer)
Use is by the hydrogenated styrene-butadiene block copolymer that obtains by preparation embodiment 2 described below.
Except the add-on of n-Butyl Lithium increased, obtaining to have with block copolymer C 5 same structures and number-average molecular weight under the condition identical with preparation embodiment 1 was 100,000 block copolymer C 6.
2-4. composition (D)
(1) D1 (rubber-modified styrene resin)
The styrene resin of the modified rubber that use obtains in following preparation embodiment 3.
Preparation embodiment 3
To be equipped with the autoclave nitrogen replacement of agitator and chuck, put into the polybutadiene latex (median size 2,500 of 50 parts (solids contents) therein
), potassium laurate and 120 parts of ion exchanged waters of 0.5 part, begin to stir.After putting into 9.2 parts of methyl methacrylates and 3.3 parts of vinylbenzene, heat up, when interior temperature reaches 40 ℃, to wherein adding 0.04 part Cumene Hydroperoxide 80 and sulfoxylic acid salt initiation adjuvant water solution with initiated polymerization.
After polymerization causes 1 hour, adding is by 27.5 parts of methyl methacrylates, 10 parts of vinylbenzene, 0.5 part of uncle's lauryl mercaptan, 0.5 part of potassium laurate and 20 parts of emulsions that ion exchanged water is formed, and carries out polyreaction while use 4 hours and add continuously 0.1 part of Cumene Hydroperoxide 80 or sulfoxylic acid salt to cause adjuvant water solution.Then, further continue to stir 2 hours, then mixture is cooled to 50 ℃ to stop polyreaction.The latex of reaction product is condensed with aqueous sulfuric acid, wash with water then, carry out drying, obtain the styrene resin D1 of modified rubber.
Its percentage of grafting is 55%, and the limiting viscosity of acetone soluble material [η] is 0.45.
(2) D2 (styrene resin that does not contain rubbery polymer)
The styrene resin that use obtains at following preparation embodiment 4.
Preparation embodiment 4
To be equipped with the autoclave nitrogen replacement of agitator and chuck, in nitrogen gas stream, put into 73.4 parts of methyl methacrylates, 26.6 parts of vinylbenzene, 20 parts of toluene and 0.1 part of uncle's lauryl mercaptan, begin to stir and heating.When interior temperature reached 50 ℃, to wherein adding 0.5 part of benzoyl peroxide, temperature further raise.After temperature reaches 80 ℃, temperature controlled constantly carry out polymerization at 80 ℃.After polymerization caused 6 hours, temperature was increased to 120 ℃ through 1 hour, further carried out polymerization in 2 hours, reaction terminating.After being cooled to 100 ℃, reaction mixture is taken out from autoclave, distill by vapor distillation then and remove unreacted matters and solvent.Product is pulverized, formed pellet after removing volatile matter with degassing extruder (vented extruder), acquisition does not contain the styrene resin D2 of rubbery polymer.Its limiting viscosity [η] is 0.45.
2-5. composition (E)
(1) E1 (aqueous solution of three (trifluoromethane sulfonyl group) lithium methide of 50%)
" SANKONOL AQ-50T " (trade(brand)name) of using Sanko chemical company to produce.
(2) E2 (static inhibitor of polymer type)
" ADECANOL AS-113 " (trade(brand)name) of using rising sun electrification company to produce, it contains 65% polymer anti static agent.
(3) E3 (the polyethylene masterbatch that contains 7% organoboron compound)
" HIGHBORON MB400N-8LDPE " (trade(brand)name) of using Boron international corporation to produce.
(4) E4 (nonionogenic tenside)
" ELECTROSTRIPPER TS-5 " (trade(brand)name) of using KAO. Corp. SA to produce, it is 100% octadecyl direactive glyceride.
2-6. composition (F)
Use Sanyo to change into polymeric amide-polyethers segmented copolymer " PELESTAT NC6321 " (trade(brand)name) that industrial produces.
2-7. composition (G) (processing aid)
Use Mitsubishi Rayon company to prepare ultra-high molecular weight acrylic polymers " METABLEN P531A " (trade(brand)name).
3. the preparation of anti-static resin composition and evaluation
Embodiment 1-1 to 1-14 and comparative example 1-1 to 1-5
After in enjoying Xie Er high speed kneader, with mentioned component (A), (B), (C) and (E) mixing, mixture is melted kneading (barrel temperature is set at 220 ℃) acquisition pellet (anti-static resin composition) in twin screw extruder with the mixture ratio of table 1 and table 2 expression.
After the pellet thorough drying, they had the tabular experiment slice of thickness 1.6mm with injection moulding machine (grain tube temperature is set at 220 ℃) moulding with acquisition.The outward appearance of anti-static function (surface resistivity), transparency and moulded product is used these experiment slice evaluations.The result is illustrated in table 1 and the table 2.
Embodiment 1-15 to 1-18
After in enjoying Xie Er high speed kneader, with mentioned component (A), (B), (C) and (E) mixing, mixture is melted kneading (barrel temperature is set at 220 ℃) acquisition pellet (anti-static resin composition) in twin screw extruder with the mixture ratio of table 3 expression.
After the pellet thorough drying, with them with extruding in the blowing forcing machine (barrel and mould temperature are set at 190 ℃ at embodiment 1-15 and 1-16, are set at 160 ℃ in embodiment 1-17 and 1-18) to obtain by having the bag that thickness 50 μ m films constitute.The outward appearance of anti-static function (surface resistivity), transparency and moulded product is used this film evaluation.The result is illustrated in the table 3.
Table 3
From table 1 to 3 obviously following as can be known contents.
All of embodiment 1-1 to 1-18 are good at anti-static function, transparency and moulded product in appearance.On the other hand, the composition among the comparative example 1-1 to 1-5 (A), (B) or content (C) are outside scope of the present invention, and their anti-static function, transparency and moulded product outward appearance are all poor.
4. the preparation of double-layer structure bag and evaluation
EXPERIMENTAL EXAMPLE 1-1
At first, 60 parts of mentioned components (A3), 26 parts of compositions (A4), 14 parts of compositions (B2) and 2 parts of compositions (E1) are mixed in enjoying Xie Er high speed kneader, then mixture is melted in twin screw extruder (barrel temperature is set at 220 ℃) and mediate to obtain pellet X (anti-static resin composition), then with its thorough drying.Afterwards, by multilayer blow moulding forcing machine (barrel and mould temperature are set at 190 ℃) coextrusion these pellets X and composition (A3).It is prepared as and forms every layer thickness is after 25 μ m and total thickness are the film of 50 μ m, and the layer of preparation anti-static resin composition is in the bag on surface.The outward appearance of transparency and moulded product is good.In addition, surface resistivity is 7 * 10
6Ω shows that anti-static function is good.
EXPERIMENTAL EXAMPLE 1-10
Except 60 parts of compositions (A3) and 26 parts of compositions (A4) are changed into 86 parts of compositions (A3) be prepared the same with EXPERIMENTAL EXAMPLE 1-1.The outward appearance of transparency and moulded product is good.In addition, surface resistivity is 1 * 10
7Ω shows that anti-static function is good.
At film (100mm * 100mm) after 1 hour, estimate its smoothness in 80 ℃ of placements of temperature with EXPERIMENTAL EXAMPLE 1-1 and EXPERIMENTAL EXAMPLE 1-10.In the film of EXPERIMENTAL EXAMPLE 1-10, observe some wrinkles, but the film in EXPERIMENTAL EXAMPLE 1-1 does not observe variation substantially.
5. preparation of three-layered node film building and evaluation
EXPERIMENTAL EXAMPLE 1-11
The pellet X and the composition (A3) that obtain with EXPERIMENTAL EXAMPLE 1-1 are raw material, and with multilayer blow moulding forcing machine (barrel and mould temperature are set at 190 ℃) preparation trilamellar membrane, wherein two upper layers are formed by anti-static resin composition (pellet X).Every layer thickness is 15/20/15 μ m.The outward appearance of transparency and moulded product is good.In addition, surface resistivity is 7 * 10
6Ω shows that anti-static function is good.
EXPERIMENTAL EXAMPLE 1-12
Except 60 parts of compositions (A3) and 26 parts of compositions (A4) are changed into 86 parts of compositions (A3), with the same being prepared of preparation of the pellet X of EXPERIMENTAL EXAMPLE 1-11.The transparency and the outward appearance of the trilamellar membrane moulded product that obtains are good.In addition, surface resistivity is 1 * 10
7Ω shows that anti-static function is good.
At film (100mm * 100mm) after 1 hour, estimate its smoothness in 80 ℃ of placements of temperature with EXPERIMENTAL EXAMPLE 1-11 and EXPERIMENTAL EXAMPLE 1-12.On the film of EXPERIMENTAL EXAMPLE 1-12, observe some wrinkles, but on the film of EXPERIMENTAL EXAMPLE 1-11, do not observe variation substantially.
6. the preparation of antistatic/pressure-sensitive-adhesive resin composition and evaluation
Embodiment 2-1 to 2-16 and comparative example 2-1
After the mixture ratio that shows with table 4 and table 5 in enjoying Xie Er high speed kneader with mentioned component (A), (B), (C) and (E) mixes, mixture melt to mediate with acquisition in two spiral shell material forcing machines (barrel temperature is set at 220 ℃) expect (antistatic/pressure-sensitive-adhesive resin composition).
After the pellet thorough drying, their moulding are obtained to have the tabular experiment slice of thickness 1.6mm by injection moulding machine (barrel temperature is set at 220 ℃).Use these experiment slices to carry out the evaluation of anti-static function (surface resistivity), transparency and moulded product outward appearance.The result is presented in table 4 and the table 5.
Can show following situation from table 4 and table 5.
All of embodiment 2-1 to 2-16 are good anti-static function, transparency and moulded product in appearance.On the other hand, in comparative example 2-1, composition (B) or content (C) have exceeded scope of the present invention, the appearance poor of anti-static function or transparency and moulded product.
7. the preparation of pressure-sensitive adhesive film and evaluation
Embodiment 3-1 to 3-17
At first, the mixture ratio that shows with table 6 to table 8 in enjoying Xie Er high speed kneader mixes to obtain to be used to form the composition of supporter with mentioned component (A), (B), (C) with (E), then composition is melted kneading with the acquisition pellet in twin screw extruder (barrel temperature is set at 220 ℃).
In addition, by mentioned component (A), (B), (C) and the mixture ratio that (E) shows with table 6 to table 8 in cylinder are mixed the composition that obtains to be used to form antistatic bonding coat.
Afterwards, use multilayer blow moulding forcing machine (barrel temperature is set at 210 to 240 ℃) to be used to form each composition coextrusion of supporter and antistatic bonding coat and to obtain pressure-sensitive pressure-sensitive adhesive film with above-mentioned, wherein supporter thickness is 50 μ m, and antistatic bondline thickness is 20 μ m.Use this pressure-sensitive adhesive film to estimate the antistatic bonding coat surface of the binding property of outward appearance, supporter and the antistatic bonding coat of supporter and each surperficial anti-static function of antistatic bonding coat, transparency and moulded product, pressure-sensitive adhesive film and the binding property of TAC film.The result shows to table 8 at table 6.
Table 6
Table 7
Table 8
As at table 6 to as shown in the table 8, all of embodiment 3-1 to 3-17 anti-static function, transparency, moulded product in appearance, be good on the binding property of the antistatic bonding coat surface of supporter and antistatic bonding coat binding property and pressure-sensitive adhesive film and TAC film.
The pressure-sensitive adhesive film of embodiment 3-12 and 3-13 (observing at 80 ℃ pressure-sensitive adhesive film after placing 1 hour by the torsion resistance of 100mm * 100mm).Observe some distortions on the pressure-sensitive adhesive film of embodiment 3-12, but on the pressure-sensitive adhesive film of embodiment 3-13, show not variation.The film that is interpreted as containing composition (A4) is good on thermotolerance.
Embodiment 3 '-1 to 3 '-13, and comparative example 3 '-1 is to 3 '-2
Pressure sensitive adhesive and each constituent of styrene resin are mixed in enjoying Xie Er high speed kneader, and fusing is mediated to obtain pellet in twin screw extruder (barrel temperature is set at 220 ℃) then.
Styrene resin is made the support film of 50 μ m by the calendering treatment process.With the one side of film through after the Corona discharge Treatment, with Corona discharge Treatment the surface on form the polymine layer.
Extrude the bonding coat that laminated method forms thickness 20 μ m by on the polymine aspect of this film, using.According to above-mentioned evaluation method, use this pressure-sensitive adhesive film to estimate the binding property of anti-static function, antistatic bonding coat and TAC film and the bond strength (binding property-2) of supporter (vinylbenzene rete) and antistatic bonding coat.Use the transparency and the outward appearance of visual evaluation film respectively.
Show from table 9 result displayed:
The embodiment of the invention 3 '-1 to 3 '-13 pressure-sensitive adhesive film is good on anti-static function, also is good on the bond strength of supporter and tackiness agent.In addition, easy control and TAC film is fusible.And they are at transparency and good in appearance film.
On the other hand, the usage quantity of composition in comparative example 3 '-1 (C) surpasses the scope of the invention, and the usage quantity of composition (B) is lower than the scope of the invention, therefore, does not show anti-static function.The usage quantity of composition in the comparative example 2 (C) is lower than the scope of the invention, and the usage quantity of composition (B) surpasses the scope of the invention, though anti-static function is not poor, the outward appearance of film is too poor and can not use in practice.
8. the preparation of three-layer tablet material and evaluation
EXPERIMENTAL EXAMPLE 1-2 to 1-9
In order to prepare the three-layer tablet material that Fig. 4 shows, the mixture ratio that shows with table 10 in enjoying Xie Er high speed kneader mixes to obtain being used to form the first layer and trilaminar composition with mentioned component (A), (B), (C) with (E), then composition is melted kneading with acquisition pellet (anti-static resin composition) in twin screw extruder (barrel temperature is set at 220 ℃).In addition, as being used to form the composition that the middle layer is the second layer, the pellet that the polymkeric substance that use is represented by table 10 constitutes.
After each pellet thorough drying mentioned above, use thickness that 2 kinds 3 layers T mould forcing machine obtains to be arranged on the second layer two sides with thickness 0.8mm all to be the first layer and the trilaminar three-layer tablet material of 0.1mm.Use this three-layer tablet material to carry out the evaluation of the outward appearance of anti-static function, transparency and moulded product.The result is presented at table 10.
Table 10 discloses all EXPERIMENTAL EXAMPLE of 1-2 to 1-9, wherein form the first layer and the 3rd layer by anti-static resin composition of the present invention in three layers of thin slice, on two surfaces excellent antistatic matter is arranged, because the second layer (middle layer) by with form the first layer and the 3rd layer of identical composition (A) forms, the outward appearance of transparency and moulded product also is good.
Therefore anti-static resin composition of the present invention is good anti-static function and moulded product in appearance, also is good on transparency, can be used as for example formed material of film and thin slice of moulded product, and described moulded product is used for the field that static causes big problem.
Antistatic/pressure-sensitive-adhesive resin composition of the present invention is good anti-static function, transparency and moulded product in appearance, therefore can be used as for example formed material of pressure-sensitive adhesive film and multi-layer sheet of moulded product, described moulded product is used for the field that static causes big problem.
The moulded product that constitutes by anti-static resin composition of the present invention and antistatic/pressure-sensitive-adhesive resin composition, for example pressure-sensitive adhesive film and multi-layer sheet, at anti-static function and moulded product is good in appearance, according to its embodiment, transparency also is good, therefore can be used as for example formed material of pressure-sensitive adhesive film and multi-layer sheet of moulded product, described moulded product is used for the field that static causes big problem.
Claims (18)
1. pressure-sensitive adhesive film, it comprises the supporter that is made of thermoplastic polymer composition, with one side, that the comprise antistatic/pressure-sensitive-adhesive resin composition at least antistatic bonding coat that is arranged on described supporter, described antistatic/pressure-sensitive-adhesive resin composition comprises:
(A) polyolefin resin except that following ingredients (B) of 0 to 59 quality %,
(B) segmented copolymer of 3 to 60 quality %, it comprises olefin polymer block and hydrophilic polymer block; With
(C) at least a polymkeric substance of 35 to 97 quality %, described polymkeric substance are selected from and comprise unitary polymkeric substance of conjugated diene compound and hydrogenated products thereof,
Condition is that mentioned component (A), (B) and summation (C) are 100 quality %.
2. the described pressure-sensitive adhesive film of claim 1 comprises: the composition of 0 to 40 quality % (A), and the composition (C) of the composition of 6 to 25 quality % (B) and 35 to 94 quality %, condition is that mentioned component (A), (B) and summation (C) they are 100 quality %.
3. the described pressure-sensitive adhesive film of claim 2, wherein, composition (A) comprises polyolefin resin (A-1) that contains 60 to 200 ℃ of cycloalkene unit and second-order transition temperatures and the polyolefin resin (A-2) that does not comprise cycloalkene unit,
Both content ratio ((A-1)/(A-2)) are 95/5 to 1/99 (quality ratio).
4. the described pressure-sensitive adhesive film of claim 2, wherein, composition (C) is at least a polymkeric substance, and described polymkeric substance is selected from segmented copolymer and the hydrogenated products thereof that comprises mainly the polymer blocks (c1) that is made of the conjugated diene compound unit and the main polymer blocks (c2) that is made of the aromatic ethenyl compound unit.
5. the described pressure-sensitive adhesive film of claim 2, wherein, described antistatic/pressure-sensitive-adhesive resin composition further comprises at least a static resistance activator (E), it is selected from following ingredients (E1), composition (E2), composition (E3) and composition (E4), its consumption is enough to improve the anti-static function of antistatic/pressure-sensitive-adhesive resin composition
Composition (E1): salt with the anionicsite that comprises the fluoro-alkyl alkylsulfonyl;
Composition (E2): comprise by following general formula (XII) and represent unitary polymkeric substance;
Composition (E3): comprise by following general formula (XIII) and represent unitary boron compound; With
Composition (E4): non-ionic tenside,
Wherein, R
5The expression alkyl, R
5 'Expression hydrogen atom, halogen atom or alkyl, X represents hydrogen atom, alkyl, has the alkyl or the hydrophilic radical of carbamate residue or ester residue, and m represents 1 or more several,
6. the described pressure-sensitive adhesive film of claim 1, wherein, described antistatic/pressure-sensitive-adhesive resin composition comprises the composition (A) of 0 to 59 quality %, the composition (C) of the composition of 3 to 60 quality % (B) and 40 to 97 quality %, wherein composition (A) is a polyolefine (A '-1) and/or by the polyolefine of functional group modification (A '-2), and composition (C) is the hydrogenated products of the polymkeric substance that mainly is made of conjugated diene compound unit and aromatic ethenyl compound unit.
7. the described pressure-sensitive adhesive film of claim 6, wherein, composition (C) is at least a polymkeric substance, and described polymkeric substance is selected from segmented copolymer and the hydrogenated products thereof that comprises mainly the polymer blocks (c1) that is made of the conjugated diene compound unit and the main polymer blocks (c2) that is made of the aromatic ethenyl compound unit.
8. the described pressure-sensitive adhesive film of claim 7, wherein, the hydrogenation ratio of the part that is made of the conjugated diene compound unit of composition (C) is 10 to 100%.
9. the described pressure-sensitive adhesive film of each of claim 1 to 5, wherein, thermoplastic polymer composition is a polyolefine resin composition.
10. the described pressure-sensitive adhesive film of claim 9, wherein, polyolefine resin composition is an anti-static resin composition, described anti-static resin composition comprises:
(A) polyolefin resin except that following ingredients (B) of 30 to 95 quality %,
(B) segmented copolymer of 5 to 20 quality %, it comprises olefin polymer block and hydrophilic polymer block; With
(C) at least a polymkeric substance of 0 to 50 quality %, described polymkeric substance are selected from and comprise the unitary polymkeric substance of conjugated diene compound and its hydrogenated products,
Condition is that mentioned component (A), (B) and summation (C) are 100 quality %.
11. the described pressure-sensitive adhesive film of claim 10, wherein, composition (A) comprises and contains cycloalkene unit and have the polyolefin resin (A-1) of 60 to 200 ℃ of second-order transition temperatures and do not comprise the polyolefin resin (A-2) of cycloalkene unit, and both content ratio ((A-1)/(A-2)) are 95/5 to 1/99 (quality ratio).
12. the described pressure-sensitive adhesive film of claim 10, wherein, composition (C) is at least a polymkeric substance, described polymkeric substance is selected from segmented copolymer and hydrogenated products thereof, and described segmented copolymer comprises polymer blocks (c1) and the main polymer blocks (c2) that is made of the aromatic ethenyl compound unit that mainly is made of the conjugated diene compound unit.
13. the described pressure-sensitive adhesive film of claim 10, wherein, described anti-static resin composition further comprises at least a static resistance activator (E), its content is enough to improve the anti-static resin composition anti-static function, it is selected from following ingredients (E1), composition (E2), composition (E3) and composition (E4)
Composition (E1): salt with the anionicsite that comprises the fluoro-alkyl alkylsulfonyl;
Composition (E2): comprise by following general formula (XII) and represent unitary polymkeric substance;
Composition (E3): comprise by following general formula (XIII) and represent unitary boron compound; With
Composition (E4): non-ionic tenside,
Wherein, R
5The expression alkyl, R
5 'Expression hydrogen atom, halogen atom or alkyl, X represents hydrogen atom, alkyl, has the alkyl or the hydrophilic group of carbamate residue or ester residue, and m represents 1 or more several,
14. the described pressure-sensitive adhesive film of each of claim 6 to 8, wherein, thermoplastic polymer composition is a composition of styrene resin.
15. be used for the protective membrane of display element, it has any one described pressure-sensitive adhesive film of claim 1 to 14.
16. the preparation method of the described pressure-sensitive adhesive film of each of claim 1 to 14, it comprises the step with described thermoplastic polymer composition and described antistatic/pressure-sensitive-adhesive resin composition coextrusion.
17. the preparation method of each described pressure-sensitive adhesive film of claim 1 to 5 and 9 to 13, wherein, thermoplastic polymer composition is a polyolefine resin composition.
18. the preparation method of the described pressure-sensitive adhesive film of each of claim 6 to 8, wherein, thermoplastic polymer composition is a composition of styrene resin.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
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| JP2005096309 | 2005-03-29 | ||
| JP2005-096309 | 2005-03-29 | ||
| JP2005244933 | 2005-08-25 | ||
| JP2005-244933 | 2005-08-25 |
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| CN2006800144143A Division CN101166784B (en) | 2005-03-29 | 2006-03-28 | Antistatic resin composition, antistatic/pressure-sensitive-adhesive resin composition, pressure-sensitive adhesive film, and method for producing the same |
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| CN101875824A true CN101875824A (en) | 2010-11-03 |
| CN101875824B CN101875824B (en) | 2014-07-23 |
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| CN201010198876.3A Expired - Fee Related CN101875824B (en) | 2005-03-29 | 2006-03-28 | Antistatic resin composition, antistatic/pressure-sensitive-adhesive resin composition, pressure-sensitive adhesive film, and process for producing the same |
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| Country | Link |
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| KR (1) | KR101243090B1 (en) |
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| JP5863157B2 (en) * | 2006-12-18 | 2016-02-16 | 日東電工株式会社 | Adhesive sheet |
| JP5168915B2 (en) * | 2007-01-24 | 2013-03-27 | テクノポリマー株式会社 | Thermoplastic polymer composition and molded article |
| EP2324388A4 (en) * | 2008-08-19 | 2016-07-20 | 3M Innovative Properties Co | Multi-layer optical articles |
| TW201250783A (en) * | 2011-03-24 | 2012-12-16 | Sumitomo Bakelite Co | Adhesive tape for processing semiconductor wafer or the like |
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| KR102477947B1 (en) * | 2020-12-29 | 2022-12-15 | 한국신발피혁연구원 | Sponge-forming composition for absorbing static electricity |
| WO2023013650A1 (en) * | 2021-08-05 | 2023-02-09 | 旭化成株式会社 | Antenna member |
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| JP4722250B2 (en) * | 2000-03-30 | 2011-07-13 | 日東電工株式会社 | Adhesive tape for marking |
| JP3616617B2 (en) * | 2001-08-24 | 2005-02-02 | 株式会社ジェイエスピー | Polyolefin resin laminate foam |
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- 2006-03-28 KR KR1020077022040A patent/KR101243090B1/en not_active IP Right Cessation
- 2006-03-28 CN CN2006800144143A patent/CN101166784B/en not_active Expired - Fee Related
- 2006-03-28 CN CN201010198876.3A patent/CN101875824B/en not_active Expired - Fee Related
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|---|---|---|---|---|
| CN103429689A (en) * | 2011-03-23 | 2013-12-04 | 阿基里斯株式会社 | Surface-protecting film |
| CN103429689B (en) * | 2011-03-23 | 2015-09-09 | 阿基里斯株式会社 | Surface protection film |
| CN114127181A (en) * | 2019-10-09 | 2022-03-01 | 大科能宇菱通株式会社 | Thermoplastic resin composition and molded article thereof |
| CN114127181B (en) * | 2019-10-09 | 2024-05-28 | 大科能宇菱通株式会社 | Thermoplastic resin composition and molded article thereof |
| CN112322233A (en) * | 2020-11-23 | 2021-02-05 | 广东能辉新材料科技有限公司 | Hot-melt pressure-sensitive adhesive containing modified SIS thermoplastic elastomer and preparation method thereof |
| CN113789003A (en) * | 2021-11-17 | 2021-12-14 | 江苏凯伦建材股份有限公司 | Self-cleaning anti-permeability waterproof sheet and preparation method and application thereof |
| CN115895136A (en) * | 2022-11-22 | 2023-04-04 | 东藤（上海）新材料有限公司 | Chip tray plastic sucking part and preparation method thereof |
| CN115895136B (en) * | 2022-11-22 | 2023-08-29 | 东藤（上海）新材料有限公司 | Chip tray plastic sucking part and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101166784B (en) | 2011-09-21 |
| KR101243090B1 (en) | 2013-03-13 |
| CN101166784A (en) | 2008-04-23 |
| KR20080002777A (en) | 2008-01-04 |
| CN101875824B (en) | 2014-07-23 |
| WO2006104133A1 (en) | 2006-10-05 |
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