CN101443404A - Antistatic resin composition and molded article - Google Patents

Abstract

The invention discloses an antistatic resin composition which comprises 40 to 98 mass% of an olefin resin (A) and 2 to 60 mass% of a block copolymer (B) having an olefin polymer block and a hydrophilic polymer block, and which can be molded into an article having a surface resistance (measured under the conditions of 23 DEG C and 50% RH) of 1x10<11> omega/square or lower and having the leaching amount of sodium and potassium ions (measured under conditions of 80 DEG C and extraction for 60 minutes) of 3 [mu]g/cm<2> or less. The composition may contain a predetermined amount of a block copolymer having an aromatic vinyl compound polymer block and a conjugated diene compound polymer block or a hydrogenation product of the block copolymer and a predetermined amount of a styrene resin. The component (B) may be a combination of a block copolymer as mentioned above which has higher sodium and potassium contents and a block copolymer as mentioned above which has lower sodium and potassium contents. If required, the composition may contain a lithium salt (E). The composition has excellent antistatic properties, chemical resistance, molded article appearance and thermal stability, and has a reduced leaching amount of ions.

Description

Anti-static resin composition and moulded product

Technical field

[0001]

The present invention relates to excellence aspect static resistance, chemical-resistant, molded article surface outward appearance and thermostability, and have the anti-static resin composition of the ion leaching amount of reduction, relate to the moulded product of making by this anti-static resin composition in addition.

Background technology

[0002]

Because polyolefin resin for example polypropylene is superior at aspects such as chemical-resistant, thermotolerance and flowabilities, so they are widely used for electric/electronic field, office automation (OA) and household appliance technical field, vehicular field, health product field etc.Yet, because these resins have their charged defectives easily, so they are difficult to use in the articles for use to the electrostatic breakdown sensitivity, for example, liquid-crystal display, plasma display, semi-conductive edge section and the various parts that in cleaning chamber, use or handle, sheet material, film etc.In order to improve such defective, the specific static inhibitor of blend has been proposed in the patent document 1 and 2, but be still debatable because static resistance is not lasting or insufficient.In addition, as the method for keeping static resistance, proposed segmented copolymer and the polyolefin resin blend that to form by polyolefin block and hydrophilic polymer block in the patent document 3, but still be a problem, because show static resistance deficiently.

[0003]

In order to improve antistatic property, generally with electrolytic component for example the salt of alkyl benzene sulphonate (ABS) and sodium, potassium etc. between polymerization period or add to afterwards in this segmented copolymer.Yet, when with electrolytic component and polyolefin resin blend, press heavy addition, because it does not show enough antistatic properties therein.The moulded product of being made by the composition that comprises this segmented copolymer and olefin resin is for aspect the leaching of above-mentioned those electrolytic component problem being arranged usually in field of liquid crystal, field of hard disks, organic EL field and LED Application for Field.Usually, also do not obtain all gratifying resin combination aspect antistatic property and ion leaching amount.

[0004]

Patent document 1: Japanese patent unexamined publication number H4-258647

Patent document 2: Japanese patent unexamined publication number 2000-313875

Patent document 3: Japanese patent unexamined publication number 2001-278985

Summary of the invention

Treat problem by the present invention's solution

[0005]

The purpose of this invention is to provide at anti-static resin composition excellent aspect the appearance of static resistance, chemical-resistant, moulded product and the thermostability and that have the ion leaching amount of reduction, and the moulded product of making by this anti-static resin composition.

The means of dealing with problems

[0006]

In order to achieve the above object, the inventor furthers investigate, so find following acquisition anti-static resin composition, the ion leaching amount aspect that is created in this anti-static resin composition enough reduces so that may be used on the moulded product of above-mentioned application: the lithium salts of predetermined amount is added in the composition that comprises olefin resin and above-mentioned segmented copolymer, or use the low or segmented copolymer that is substantially free of these elements of sodium and/or potassium content as above-mentioned segmented copolymer, or for example sodium and/or the potassium content segmented copolymer higher than preceding a kind of multipolymer use in combination with this segmented copolymer and another kind of segmented copolymer.In addition, have been found that when with said composition and styrene resin with comprise the polymer blocks formed by aromatic vinyl compound and during the segmented copolymer blend of the polymer blocks be made up of conjugated diene compound or its hydrogenated products, static resistance is improved and ion leaching amount is reduced.Therefore, finished the present invention.

Promptly, according to one aspect of the invention, anti-static resin composition (hereinafter to be referred as the ＂ first anti-static resin composition ＂) is provided, it comprises following component of 40-98 quality % (A) and the following component of 2-60 quality % (B), condition is that said modules (A) and total amount (B) are 100 quality %, wherein when said composition was molded as goods, described composition had 1 * 10 ¹¹Ω/ or lower surface resistivity (under the condition of 23 ℃ and 50%R.H., measuring) and 3 μ g/cm ²Or lower sodium and potassium ion leaching amount (under the condition of 80 ℃ and extraction in 60 minutes, measuring).

Component (A): olefin resin; With

Component (B): the segmented copolymer that comprises olefin polymer block and hydrophilic polymer block.

First anti-static resin composition embodiment preferred according to the present invention, said components (B) is that total content that 1/99-90/10 comprises sodium and potassium is that the total content of the segmented copolymer (B-1) of 500-8000ppm and sodium and potassium is the segmented copolymer (B-2) of 0-100ppm and to account for this segmented copolymer of amount blend (B-1) of said components (A) and total amount 1-15 quality % (B) by segmented copolymer (B-1) with respect to the mass ratio of segmented copolymer (B-2).Be included in component (B), the sodium and/or the potassium that particularly are included in the above-mentioned segmented copolymer (B-1) preferably are sulfonate form.

In addition, another embodiment preferred of first anti-static resin composition according to the present invention, except said components (A) with (B), it also comprises 0.01-5 mass parts lithium salts (E), with respect to 100 mass parts said components (A) and total amounts (B).In this case, the total content of sodium and potassium preferably 0-1000ppm, more preferably 0-100ppm in the said components (B).When said components (B) comprised sodium and/or potassium, it is involved that they preferably press the form of sulfonate.

In addition, according to a further aspect of the present invention, anti-static resin composition (hereinafter to be referred as the ＂ second anti-static resin composition ＂) is provided, it comprises the following component of 7-91 quality % (A), the following component of 2-60 quality % (B), the following component of 2-50 quality % (C) and the following component of 5-50 quality % (D), condition is that said components (A), (B), (C) and total amount (D) are 100 quality %, and wherein said composition has 1 * 10 ¹¹Ω/ or lower surface resistivity (under the condition of 23 ℃ and 50%R.H., measuring) and 3 μ g/cm ²Or lower sodium and potassium ion leaching amount (under the condition of 80 ℃ and extraction in 60 minutes, measuring).

Component (A): olefin resin;

Component (B): the segmented copolymer that comprises olefin polymer block and hydrophilic polymer block;

Component (C): at least a elastomerics, it is selected from the segmented copolymer of the polymer blocks that comprises mainly the polymer blocks is made up of aromatic vinyl compound and mainly be made up of conjugated diene compound and its hydrogenated products; With

Component (D): styrene resin, its rubber that comprises by make the polymerization of vinyl monomer acquisition that comprises aromatic vinyl compound in the presence of rubbery polymer strengthens styrene polymer (D-1), and/or (being total to) polymkeric substance (D-2) of described vinyl monomer.

Second anti-static resin composition embodiment preferred according to the present invention, said components (B) is that 1/99-90/10 comprises above-mentioned segmented copolymer (B-1) and above-mentioned segmented copolymer (B-2) by segmented copolymer (B-1) with respect to the mass ratio of segmented copolymer (B-2), and to account for this segmented copolymer of amount blend (B-1) of said components (A), (B), (C) and total amount 1-15 quality % (D).Be included in said components (B), the sodium and/or the potassium that particularly are included in the above-mentioned segmented copolymer (B-1) preferably are sulfonate form.

In addition, another embodiment preferred of second anti-static resin composition according to the present invention, except said components (A), (B), (C) and (D) outside, it also comprises 0.01-5 mass parts lithium salts (E), with respect to 100 mass parts said components (A), (B), (C) and total amount (D).In this case, the total content of sodium and potassium preferably 0-1000ppm, more preferably 0-100ppm in the said components (B).When said components (B) comprised sodium and/or potassium, it is involved that they preferably press the form of sulfonate.

When adding to lithium salts (E) in first and second anti-static resin compositions, lithium salts to be used (E) is preferably selected from lithium perchlorate, trifluoromethayl sulfonic acid lithium, two (trifluoromethane sulphonyl) imines lithiums and three (trifluoromethane sulfonyl group) methane lithium at least a.

In addition, according to a further aspect of the present invention, the moulded product made by above-mentioned anti-static resin composition for example sheet material and film are provided.

Hereinafter, when general designation first anti-static resin composition of the present invention and second anti-static resin composition, use ＂ anti-static resin composition ＂ of the present invention.

In addition, sodium among the present invention and potassium ion leaching amount are meant the total amount of the leaching amount of the leaching amount of sodium ion and potassium ion, and arbitrary in the described leaching amount can be 0, or described leaching amount can surpass 0.

Effect of the present invention

[0007]

According to the present invention, lithium salts by adding predetermined amount and/or use as multiple segmented copolymer bonded segmented copolymer has reduced the sodium and the potassium content that comprise with the anti-static resin composition of the olefin resin of the segmented copolymer blend that contains olefin polymer block and hydrophilic polymer block.Therefore, provide excellent aspect chemical-resistant, molded article surface outward appearance and the thermostability and be created in the anti-static resin composition of good isostatic moulded product between static resistance and sodium and the potassium ion leaching amount.

Preferred forms of the present invention

[0008]

Hereinafter, will describe the present invention in detail.In this manual, term ＂ (being total to) polymkeric substance ＂ is meant homopolymer and multipolymer, and term ＂ (methyl) acryl ＂ is meant acryl and/or methacryloyl, and term ＂ (methyl) acrylate ＂ is meant acrylate and/or methacrylic ester.

[0009]

The explanation of first anti-static resin composition

The component of anti-static resin composition of the present invention (A) is olefin resin (A).For example, olefin resin (A) comprises by at least a olefin resin that constitutes that is selected from the alkene that contains 2-10 carbon atom, gets rid of (being total to) polymkeric substance of the component of describing after a while (B).These olefin resins (A) can use individually or two or more use in combination.

The alkene that is used to prepare above-mentioned olefin resin (A) for example comprises that ethene and alpha-olefin be propylene, butene-1, amylene-1, hexene-1,3-methyl butene-1,4-methylpentene-1 and 3-methyl hexene-1 for example, and comprises for example norbornylene of cyclic olefin.They can use individually or two or more use in combination.In the middle of them, preferably ethene, propylene, butene-1,3-methyl butene-1,4-methylpentene-1 and norbornylene.

Other monomer that can randomly be used to prepare olefin resin (A) for example comprises that non-conjugated diene is the 4-methyl isophthalic acid for example, 4-hexadiene, 5-methyl isophthalic acid, 4-hexadiene, 7-methyl isophthalic acid, 6-octadiene and 1,9-decadiene.

[0010]

The preferably main polymkeric substance of being made up of propylene units of olefin resin (A) is polypropylene and propylene-ethylene copolymers and polyethylene and ethylene-norbornene copolymer for example.They can use individually or in combination.Simultaneously,, can use in random copolymers, the segmented copolymer etc. any as aforesaid propylene-ethylene copolymer, and for the consideration of molded article surface outward appearance especially preferably being used random.In addition, as polyethylene, can use in high density polyethylene(HDPE), new LDPE (film grade), the linear low density polyethylene etc. any.

Be used for olefin resin of the present invention and can be by the known polymerization process olefin resin of high pressure polymerization process, low-pressure polymerization method and the preparation of metallocene catalyst polymerization process for example.

In addition, being used for olefin resin of the present invention can be that polymerizing catalyst is removed catalytic olefin resin, or with the olefin resin of modifications such as acid anhydrides, carboxyl, epoxy group(ing).

[0011]

As olefin resin (A), can use crystalline or amorphous olefin resin, but preferred use has at room temperature by what X-ray diffraction was measured and is no less than at least a in those of 10% degree of crystallinity.

As olefin resin (A), what preferably use is to have the olefin resin of measuring according to JIS K7121 that is no less than 40 ℃ fusing point.

When using acrylic resin as component of the present invention (A), it should have preferred 0.01-500g/10min, more preferably 0.05-100g/10min's adopts the melt flow rate (MFR) of the load measurement of 2.16kg according to JIS K7210:1999 under 230 ℃ temperature, with when using polyvinyl resin, it should have preferred 0.01-500g/10min, and more preferably 0.05-100g/10min's adopts the melt flow rate (MFR) of the load measurement of 2.16kg according to JIS K6922-2 under 190 ℃ temperature.

[0012]

As olefin resin of the present invention, can use wherein blend various additives for example antioxidant, thermo-stabilizer and lubricant olefin resin or wherein do not have the olefin resin of blend additive.For some application, it will be the gaseous component that produces from moulded product that preferred sometimes use does not wherein have the above-mentioned various components of additives of blend (A), described various additives fully.

[0013]

The amount to be used that constitutes the component (A) of the present invention's first anti-static resin composition is 40-98 quality %, preferred 45-97 quality %, further preferred 45-95 quality %, especially preferred 50-95 quality %, condition is that component of the present invention (A) and total amount (B) they are 100 quality %.When this measured less than 40 quality %, thermostability was relatively poor; When it surpassed 98 quality %, static resistance was relatively poor.

For requiring the excellent chemical-resistant and the application of molded article surface outward appearance, the amount to be used of component (A) is 60-98 quality % preferably, further preferred 65-97 quality %, further preferred 65-95 quality %, especially preferred 70-95 quality %, condition is that component of the present invention (A) and total amount (B) are 100 quality %.When this measured less than 60 quality %, the chemical-resistant of moulded product and appearance were often relatively poor.For requiring the excellent antistatic property and the application of thermostability, the amount to be used of component (A) is 40-70 quality % preferably, further preferred 50-65 quality %, and condition is that component of the present invention (A) and total amount (B) they are 100 quality %.When said composition as having excellent anti static behaviour and smooth surface and aspect the sheet surface outward appearance during upper layer of outstanding foam layer compressing tablet, the amount to be used of component (A) is 40-80 quality % preferably, further preferred 50-70 quality %, condition is that component of the present invention (A) and total amount (B) are 100 quality %.

[0014]

The component (B) relevant with anti-static resin composition of the present invention is the segmented copolymer that comprises olefin polymer block (B-a) and hydrophilic polymer block (B-b), and preferably low aspect sodium and/or potassium content.The component (B) that reduces aspect sodium and/or potassium content can be by for example, constitute as component (B) with segmented copolymer (B-2) bonded segmented copolymer (B-1), this segmented copolymer (B-1) is height aspect the content of sodium and/or potassium, and this segmented copolymer (B-2) is lower or do not contain these elements than segmented copolymer (B-1) aspect the content of sodium and/or potassium.Perhaps, can use by sodium compound and/or potassium compound that between polymerization period, uses the reduction amount or the component (B) of not using these compound.

Component of the present invention (B) can be a diblock, maybe can be to have three or many blocks of more blocks.Olefin polymer block (B-a) is (being total to) polymkeric substance of alkene.Alkene for example comprises as used herein, ethene and alpha-olefin be propylene, butene-1, hexene-1,3-methyl butene-1,4-methylpentene-1 and 3-methyl hexene-1 for example, and comprise for example norbornylene of cyclic olefin, optimal ethylene, propylene, butene-1,3-methyl butene-1,4-methylpentene-1 and norbornylene.They can use individually or two or more use in combination.In addition, non-conjugated diene is the 4-methyl isophthalic acid for example, 4-hexadiene, 5-methyl isophthalic acid, and 4-hexadiene, 7-methyl isophthalic acid, 6-octadiene and 1, the 9-decadiene can be as the part of this polymeric constituent.The number-average molecular weight of olefin polymer block (B-a) is 800-20 preferably, and 000, more preferably 1,000-10,000, especially preferred 1,200-6,000, (GPC) measures and changes into the polystyrene equivalent by gel permeation chromatography.

[0015]

Above-mentioned olefin polymer block (B-a) basically with above-mentioned block (B-b) keyed jointing.They are via at least a keyed jointing that is selected from ester bond, amido linkage, ehter bond, urethane bond, the imide bond etc.Wherein they press the structure of alternately repeated mode via these key keyed jointings in this block formation.

Therefore, the molecular end of above-mentioned block (B-a) must pass through functional group modification, this functional group can with the functional group reactions of two molecular ends of above-mentioned block (B-b).These functional groups for example comprise, carboxyl, hydroxyl, amino, anhydride group, oxazolinyl, epoxy group(ing) etc.

Component of the present invention (B-a) can obtain by polymerization process and thermal destruction method.The polyolefine that obtains by polymerization process can prepare by ordinary method.For example, can in the presence of free radical catalyst, metal oxide catalyst, Z-type catalyst, Ziegler-Natta catalyst, metalloscene catalyst etc., (being total to) polymerization by above-mentioned alkene easily obtain.On the other hand, can easily for example pass through the method preparation of describing among the Japanese patent unexamined publication number H3-62804 by the low-molecular-weight polyolefin that high molecular polyolefine obtains by the thermal destruction method.The thermal destruction method is preferred, because the easy modification of above-mentioned molecular end.

[0016]

The polyolefine that obtains by the thermal destruction method normally have two correctability molecular ends polyolefine, have the polyolefine of a correctability end and without any the polyolefinic mixture of correctability end, and preferably mainly form by polyolefine with two correctability ends.

For the consideration to antistatic property, the two key amounts in the polyolefine that obtains by the thermal destruction method are 1-40 preferably, further preferred 2-30, especially preferred 4-20/1,000 carbon atom.

For to formation property of repeating structure and the consideration of antistatic property, the average double key number in each molecule is 1.1-5 preferably, further preferred 1.3-3, especially preferred 1.8-2.2.

In the thermal destruction method, can easily obtain average terminal double link number, Mn=800-6 that each molecule has 1.5-2,000 low-molecular-weight polyolefin is (referring to for example, KatsuhideMURATA, Tadahiko MAKINO, Nippon Kagaku Kaishi, 1975, p192).

[0017]

The preferred method of giving functional group for these polyolefine that obtain by the thermal destruction method is that the carbon carbon unsaturated compound that will have above-mentioned functional group adds at its molecular end and has method on the thermal destruction component (B-a) of carbon-to-carbon double bond.

[0018]

The hydrophilic polymer of above-mentioned block component (B-b) for example comprises, polyethers, the hydrophilic polymer that contains polyethers and anionic polymer.

Polyethers comprises polyether Glycols, polyether diamine and its modified product.

The hydrophilic polymer that contains polyethers comprises having polyether Glycols segmental polyether ester amides, have polyether Glycols segmental polyetheramides imide, have polyether Glycols segmental polyether ester, have polyether diamine segmental polyetheramides, have polyether Glycols or polyether diamine segmental polyethers urea alkane.

Anionic polymer comprises that containing the dicarboxylic acid with alkylsulfonyl constitutes the anionic polymer of unit and above-mentioned polyethers as necessity, and preferably has 2-80 alkylsulfonyl, more preferably 3-60 alkylsulfonyl in its molecule.They can be linearity or branching.Especially preferred component (B-b) is a polyethers.

[0019]

Polyether Glycols as polyethers for example comprises, by those of general formula (I) expression:

H-(OA ¹) _n-O-E ¹-O(A ¹O) _n＇-H

With by those of general formula (II) expression:

H-(OA ²) _m-O-E ²-O-(A ²O) _m＇-H

In general formula (I), E ¹Representative is removed hydroxyl and the residue that produces from the bivalent compound of hydroxyl, A ¹Be the alkylidene group that contains 2-4 carbon atom, n and n ' represent the number with respect to the oxyalkylene of the hydroxyl institute addition of the bivalent compound of hydroxyl separately.(OA ¹) n unit and (A ¹O) the individual unit of n ' can be identical or different, and when they are made of two or more oxyalkylenes, and this group can be by the mode keyed jointing of block, random or its combination.Normally, n and n ' generally are 1-300, preferred 2-250, the integer of especially preferred 10-100.In addition, n and n ' can be identical or different.

[0020]

The bivalent compound of above-mentioned hydroxyl comprises the compound that contains two alcohol or phenolic hydroxyl group in the molecule, it is dihydroxy compound, particularly including dibasic alcohol (aliphatic series, alicyclic ring and the aromatic diol that for example, contain 2-12 carbon atom), contain the dihydric phenol of 6-18 carbon atom and the dibasic alcohol of tertiary-amino-containing.

The example of aliphatic diol comprises aklylene glycol for example ethylene glycol and propylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol, 1,12-dodecanediol etc.

The example of alicyclic ring dibasic alcohol comprises 1,2-and 1, and 3-encircles pentanediol, 1,2,1,3-and 1,4-cyclohexanediol and 1,4 cyclohexane dimethanol.The example of aromatic diol comprises xylyl alcohol etc.

The example of dihydric phenol comprises monocycle dihydric phenol for example quinhydrones, catechol, Resorcinol and laccol, and bis-phenol is dihydroxyphenyl propane, Bisphenol F, bisphenol S for example, 4,4 '-dihydroxyl phenylbenzene-2, the 2-butane, dihydroxybiphenyl, dihydroxy diphenyl ether and fused polycycle dihydric phenol be dihydroxy naphthalene and dinaphthol for example.

[0021]

In general formula (II), E ²The residue of representative from removing hydroxyl as the bivalent compound of the hydroxyl mentioned the general formula (I) and producing, A ²Be the alkylidene group that replaces, its at least a portion is represented by general formula (III) :-CHR-CHR '-[wherein one of R and R ' are the group by general formula (IV) expression :-CH ₂O (A ³O) xR ", another is H, in general formula (IV), x is the integer of 1-10, R " and be H or alkyl, aryl, alkaryl, aralkyl or the acyl group that contains 1-10 carbon atom, A ³Be the alkylidene group that contains 2-4 carbon atom], remaining A of while ²It can be the alkylidene group that contains 2-4 carbon atom.(OA ²) m unit and (A ²O) m ' unit can be identical or different.Preferably, m and m ' are 1-300, further preferred 2-250, the integer of especially preferred 10-100.In addition, m and m ' can be identical or different.

[0022]

Polyether Glycols by above-mentioned general formula (I) expression can be by preparing the oxyalkylene addition reaction to the binary compound of hydroxyl.As oxyalkylene, use the oxyalkylene contain 2-4 carbon atom, for example comprise ethylene oxide, propylene oxide, oxidation 1,2-butylene, oxidation 1,4-butylene, oxidation 2,3-butylene and oxidation 1,3-butylene, and two or more combination in them.When using two or more oxyalkylenes, they can be by any keyed jointing in random and/or the block fashion.Preferred oxyalkylene is independent ethylene oxide and ethylene oxide and can be by the combination of the another kind of oxyalkylene of block and/or random fashion addition.The number for the treatment of the oxyalkylene of addition is a preferred 1-300 of hydroxyl with respect to the binary compound of above-mentioned hydroxyl, more preferably 2-250, the especially preferably integer of 10-100.

[0023]

Preferred embodiment by the preparation method of the polyether Glycols of above-mentioned general formula (II) expression comprises following method (1) and (2).

[0024]

(1) wherein with the binary compound of above-mentioned hydroxyl as parent material and the glycidyl ether polymerization of representing by logical formula V:

[0025]

[in logical formula V, A ⁴Be the alkylidene group that contains 2-4 carbon atom, p is the integer of 1-10, R ¹Be H or the alkyl that contains 1-10 carbon atom, aryl, alkaryl, aralkyl or acyl group], and randomly with the method for the oxyalkylene copolymerization that contains 2-4 carbon atom.

[0026]

(2) wherein use the binary compound of hydroxyl to prepare the method for polyether Glycols via the polyethers that on side chain, contains the chloro methyl as parent material.More particularly, addition copolymerization by Epicholorohydrin or Epicholorohydrin and oxyalkylene obtains to contain the polyethers of chloro methyl on side chain, be prepared as follows this polyether Glycols then: the polyethers that obtains above making in the presence of alkali and contain the polyalkylene glycol and the R of 2-4 carbon atom ¹X (R wherein ¹As mentioned above; X represents chlorine, bromine or iodine) reaction, or polyethers that obtains above in the presence of alkali, making and polyalkylene glycol mono alkyl (monocarbyl) the ether reaction that contains 2-4 carbon atom.

As the oxyalkylene for the treatment of to contain as used herein 2-4 carbon atom, can use above-mentioned owning.

Preferred ingredients (B) can obtain above-mentioned olefin polymer block (B-a) and above-mentioned hydrophilic polymer block (B-b) polymerization by ordinary method.For example, can be by under 200-250 ℃, under reduced pressure carrying out the polyreaction preparation of polymer blocks (B-a) and polymer blocks (B-b).In addition, can during polyreaction, use conventional polymerizing catalyst.

[0027]

Operable conventional polymerizing catalyst preferably is selected from one or both or the more kinds of combinations in the following catalyzer during polyreaction: tin-based catalyst is oxidation monobutyl tin for example, antimony-based catalyst is ANTIMONY TRIOXIDE SB 203 99.8 PCT and tellurium dioxide for example, Ti-base catalyst is tetrabutyl titanate for example, Zirconium-base catalyst is zirconium hydroxide, zirconium white and zirconium acetate and IIB family organic acid salt catalyzer for example.

[0028]

In order to improve static resistance, the compound (B-1-1) that will contain sodium and/or potassium is introduced component (B), particularly component (B-1).This compound can be introduced wherein between the polymerization period of component (B), particularly component (B-1) or afterwards, or introduces by the mode of using these opportunitys simultaneously, and the method that preferably wherein allows this kind compound to exist between polymerization period.

The salt that component (B-1-1) comprises sodium and potassium for example with the salt and the halogenide of organic acid, sulfonic acid and mineral acid.

[0029]

The halogenide that the concrete preferred embodiment of component (B-1-1) comprises sodium or potassium is sodium-chlor, Repone K, Sodium Bromide and Potassium Bromide for example; The inorganic acid salt of sodium or potassium is sodium perchlorate and potassium perchlorate for example; The organic acid salt of sodium or potassium is sodium acetate, potassium acetate, sodium stearate and potassium stearate for example; Alkylsulphonic acid with the alkyl that contains 8-24 carbon atom is the sodium or the sylvite 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 sulfonic acid is the sodium or the sylvite of phenylbenzimidazole sulfonic acid and naphthyl sulfonic acid for example; Alkyl benzene sulphonate (ABS) with the alkyl that contains 6-18 carbon atom is the sodium or the sylvite of octyl group Phenylsulfonic acid, Witco 1298 Soft Acid, dibutyl Phenylsulfonic acid and dinonyl Phenylsulfonic acid for example; Alkyl naphthalene sulfonic acid with the alkyl that contains 2-18 carbon atom is the sodium salt or the sylvite of dimethylnaphthalene sulfonic acid, di-isopropyl naphthene sulfonic acid and dibutyl naphthene sulfonic acid for example; Fluorinated sulfonic is the sodium of trifluoromethane sulfonic acid or sylvite etc. for example.They can use individually or two or more use in combination.Especially preferred component (B-1-1) is the compound that is the sulfonate form of sodium and/or potassium, particularly including with the sodium salt compound of sulfonic acid or with the potassium salt compound of sulfonic acid.

When component of the present invention (B) by said components (B-1) and (B-2) constitutes, with respect to 100 mass parts component of the present invention (B-1), can preferably press the 0.1-20 mass parts, the amount use said components (B-1-1) of further preferred 1-15 mass parts.The total content of middle sodium of component of the present invention (B-1) and potassium is 500-8000ppm preferably, and wherein component (B-1) can not contain arbitrary this two kinds of elements that maybe can comprise in these elements.

When adding to lithium salts (E) in the anti-static resin composition of the present invention, the total content of middle sodium of component (B) and potassium is 0-1000ppm preferably, more preferably 0-500ppm, especially preferred 0-100ppm, wherein component (B) can not contain arbitrary this two kinds of elements that maybe can comprise in sodium and the potassium.

In sodium and the potassium content of each can by based on the amount of during the preparation of the present composition, adding as calculated or by obtaining with measurement present compositions such as x-ray fluorescence analysis, atomic absorption spectrometrys.

[0030]

The ratio of component (B-a) in the component of the present invention (B-1)/component (B-b) is 10-90/10-90 quality % preferably, further preferred 20-80/20-80 quality %, especially preferred 30-70/30-70 quality %.

This kind segmented copolymer (B-1) can for example pass through, the method preparation of mentioning among Japanese patent unexamined publication number 2001-278985 and the 2003-48990.Component of the present invention (B-1) also can be used as Sanyo Chemical Industries, and 230 of the ＂ PELESTAT ＂ 300 of 300 series of Ltd. preparation and 303 and 200 series obtain.

[0031]

Component of the present invention (B-2) is the component that contains the content reduction of sodium and/or potassium compound (B-1-1) or do not contain this compound (B-1-1), and this compound (B-1-1) is included in the said components (B-1) to improve static resistance.Relate to the whole of component (B-1) description and can be used for this, and they can use individually or two or more use in combination.For example, component (B-2) can obtain by carrying out polymerization with the sodium of reduction amount and/or potassium compound (B-1-1) or do not use compound (B-1-1) to carry out polymerization.The total content of middle sodium of component of the present invention (B-2) and potassium is 0-100ppm preferably, and wherein component (B-2) can not contain arbitrary this two kinds of elements that maybe can comprise in these elements.

Even when adding to lithium salts (E) in the anti-static resin composition of the present invention, in order further to improve antistatic property, component (B) preferably contains the content reduction of sodium and/or potassium compound (B-1-1) or does not contain the component of this compound (B-1-1).As preferred ingredients (B), can use said components (B-2).

The component that sodium and potassium content are low (B) can or only be obtained by component (B-2) by component (B-1) and component (B-2), so that sodium and potassium leaching amount preferably can be reduced to 2 μ g/cm ²Or lower, more preferably 1 μ g/cm ²Or lower, especially preferably can not detected level.

[0032]

In first anti-static resin composition of the present invention, with respect to 100 quality % component (A) and total amounts (B), the amount of component (B) is 2-60 quality %, preferred 3-55 quality %, further preferred 5-55 quality %, especially preferred 5-50 quality %.When this measured less than 2 quality %, antistatic property was relatively poor; When it surpassed 60 quality %, thermostability was relatively poor, and in some cases, ionic leaching amount increases.

For requiring the excellent chemical-resistant and the application of molded article surface outward appearance, with respect to 100 quality % component (A) and total amounts (B), the amount of component (B) is 2-40 quality % preferably, more preferably 3-35 quality %, further more preferably 5-35 quality %, especially preferred 5-30 quality %.When this amount surpassed 40 quality %, chemical-resistant and appearance were often relatively poor.For requiring the excellent antistatic property and the application of thermostability, with respect to 100 quality % component (A) and total amounts (B), the amount of component (B) is 30-60 quality % preferably, more preferably 35-50 quality %.When said composition as having excellent anti static behaviour and smooth surface and aspect the sheet surface outward appearance during upper layer of outstanding foam layer compressing tablet, the consumption of component (B) is 20-60 quality % preferably, further preferred 30-50 quality % is with respect to 100 quality % component (A) and total amounts (B).

When component (B) is made of said components (B-1) and component (B-2), component (B-1) is with respect to the mass ratio to be used of component (B-2) 1/99-90/10 preferably, more preferably 2/98-85/15, further preferred 10/90-85/15, further more preferably 15/85-80/20, especially preferred 20/80-75/25.In this scope, static resistance and ionic leaching amount obtain balanced especially well.

In order to improve antistatic property, the usage quantity that improves component (B-1) is effectively, but not preferred, because sodium and potassium are from the leaching amount increase of moulded product.Therefore, the amount to be used of component (B-1) 1-15 quality % preferably in the present invention's first anti-static resin composition, more preferably 3-13 quality %, further more preferably 5-10 quality %, especially preferred 5-9 quality % is with respect to 100 quality % component (A) and total amounts (B).

According to the present invention, by component (B-1) and the component (B) that (B-2) constitutes provide to satisfy and have 1 * 10 ¹¹Ω/ or lower, preferred 5 * 10 ¹⁰Ω/ or lower surface resistivity (under the condition of 23 ℃ and 50%R.H., measuring) and 3 μ g/cm ²Or the moulded product of the requirement condition of lower sodium and potassium ion leaching amount (under the condition of 80 ℃ and extraction in 60 minutes, measuring), thereby antistatic property and ion are equilibrated to than higher in the past degree between leaching.In ordinary method, the blending amount that increases said components (B-1) to be improving antistatic property, but in this case, often leaches from the ion of moulded product and improves.On the contrary, according to the present invention, for example,, can obtain antistatic property and ion and leach height equilibrated moulded product by using common obtainable component (B-1) in combination with unavailable component (B-2) also.Use component (B-1) in combination and (B-2) can make the leaching amount of sodium ion and potassium ion be reduced to preferred 2 μ g/cm as component (B) ²Or lower, more preferably 1 μ g/cm ²Or it is lower.

[0033]

The component (E) relevant with anti-static resin composition of the present invention is lithium salts, and can obtain the improvement effect of antistatic property by this component of blend.

The preferred lithium salts (E) that uses comprises lithium perchlorate, trifluoromethayl sulfonic acid lithium, two (trifluoromethane sulphonyl) imines lithium and three (trifluoromethane sulphonyl) methane lithium, and further trifluoromethayl sulfonic acid lithium preferably.They can use individually or two or more use in combination.They can be used as the Co. by Sanko Chemical, and SANKONOL 0862-13T, the AQ-50T of Ltd. preparation, AQ-75T, TBX-25 (trade(brand)name) obtain with solution or master batch form.

Component in first anti-static resin composition (E) is by preferred 0.01-5 mass parts, further preferred 0.1-3 mass parts, and especially preferred 0.3-2 mass parts is used, with respect to 100 mass parts components (A) and (B).When its amount to be used during less than 0.01 mass parts, be unreachable to the improvement effect of antistatic property, when it surpassed 5 mass parts, shock-resistance often reduced.

In addition, provide satisfied with lithium salts (E) and the first anti-static resin composition blend of the present invention and have 1 * 10 ¹¹Ω/ or lower, preferred 1 * 10 ¹⁰Ω/ or lower surface resistivity (under the condition of 23 ℃ and 50%R.H., measuring) and 3 μ g/cm ²Or lower, the moulded product of the requirement condition of sodium that preferably can not detection limit and potassium ion leaching amount (under the condition of 80 ℃ and extraction in 60 minutes, measuring), thus antistatic property and ion are equilibrated to than higher in the past degree between leaching.In ordinary method, the blending amount that increases said components (B) to be improving antistatic property, but in this case, often improves from the ion leaching amount of moulded product.On the contrary, according to the present invention, can by the lithium salts of blend predetermined amount and randomly use sodium and/or potassium content is low or the component that is substantially free of these elements as component (B), can obtain antistatic property and ion and leach height equilibrated moulded product.

[0034]

The explanation of second anti-static resin composition

Second anti-static resin composition of the present invention also comprises component (C) and (D) except first anti-static resin composition, and the balance between therefore antistatic property and ion leach is improved and the shock-resistance height.

In second anti-static resin composition of the present invention, component (A) can be any in the above-mentioned olefin resin (A), and they can use individually or two or more use in combination.

[0034]

The amount to be used of component (A) is 7-91 quality % in the present invention's second anti-static resin composition, preferred 10-85 quality %, more preferably 15-80 quality %, further more preferably 15-70 quality %, especially preferred 15-65 quality % is with respect to 100 quality % components of the present invention (A), (B), (C) and total amount (D).When its amount to be used during less than 7 quality %, shock-resistance and static resistance are relatively poor; When it surpassed 91 quality %, antistatic property and shock-resistance were relatively poor.

For the application that requires excellent chemical moral character and molded article surface outward appearance, the amount to be used of component (A) is 10-85 quality % preferably, further preferred 20-80 quality %, especially preferred 30-75 quality % is with respect to 100 quality % components (A), (B), (C) and total amount (D).When its amount to be used during less than 30 quality %, the chemical-resistant of moulded product and appearance are often relatively poor.

For requiring the excellent antistatic property and the application of thermostability, the amount of component to be used (A) is 7-40 quality % preferably, and further preferred 10-35 quality % is with respect to 100 quality % components (A), (B), (C) and total amount (D).When said composition as having excellent anti static behaviour and smooth surface and aspect the sheet surface outward appearance during upper layer of outstanding foam layer compressing tablet, the amount to be used of component (A) is 7-30 quality % preferably, further preferred 7-25 quality % is with respect to 100 quality % components (A), (B), (C) and total amount (D).

In second anti-static resin composition of the present invention, component (B) can be any in the said components (B), and they can use individually or two or more use in combination.

[0036]

The amount to be used of component (B) is 2-60 quality % in the present invention's second anti-static resin composition, preferred 3-55 quality %, more preferably 5-55 quality %, especially preferred 5-50 quality % is with respect to 100 quality % components of the present invention (A), (B), (C) and total amount (D).When this measured less than 2 quality %, antistatic property was relatively poor; When it surpassed 60 quality %, thermostability was relatively poor.For the application that requires excellent chemical moral character and molded article surface outward appearance, the amount to be used of component (B) is 2-40 quality % preferably, more preferably 3-35 quality %, further preferred 5-35 quality %, especially preferred 5-30 quality % is with respect to 100 quality % components (A), (B), (C) and total amount (D).When this amount surpassed 40 quality %, the appearance of moulded product and shock-resistance were often relatively poor.For requiring the excellent antistatic property and the application of thermostability, the amount of component to be used (B) is 30-60 quality % preferably, and further preferred 35-50 quality % is with respect to 100 quality % components (A), (B), (C) and total amount (D).When said composition as having excellent anti static behaviour and smooth surface and aspect the sheet surface outward appearance during upper layer of outstanding foam layer compressing tablet, the amount to be used of component (B) is 20-60 quality % preferably, further preferred 30-60 quality %, especially preferred 40-60 quality % is with respect to 100 quality % components (A), (B), (C) and total amount (D).

When component (B) is made of said components (B-1) and component (B-2), component (B-1) is with respect to the mass ratio to be used of component (B-2) 1/99-90/10 preferably, more preferably 2/98-85/15, further preferred 10/90-85/15, further more preferably 15/85-80/20, especially preferred 20/80-75/25.In this scope, the balance between static resistance and ion leaching amount is excellent especially.

In order to improve antistatic property, the consumption that improves component (B-1) is effectively, but not preferred, because sodium and potassium are from the leaching amount increase of moulded product.Therefore, the amount of component (B-1) to be used 1-15 quality % preferably in the present invention's second anti-static resin composition, more preferably 3-13 quality %, further more preferably 5-10 quality %, especially preferred 5-9 quality % is with respect to component (A), (B), (C) and total amount (D).

According to the present invention, provide to satisfy to have 1 * 10 ¹¹Ω/ or lower, preferred 5 * 10 ¹⁰Ω/ or lower surface resistivity (under the condition of 23 ℃ and 50% R.H., measuring) and 3 μ g/cm ²Or the moulded product of the requirement condition of lower sodium and potassium ion leaching amount (under the condition of 80 ℃ and extraction in 60 minutes, measuring), thereby antistatic property and ion are equilibrated to than higher in the past degree between leaching.In ordinary method, the blending amount that increases said components (B-1) to be improving antistatic property, but in this case, often leaches from the ion of moulded product and improves.On the contrary, according to the present invention, for example,, can obtain antistatic property and ion and leach height equilibrated moulded product by using common obtainable component (B-1) in combination with unavailable component (B-2) also.Use component (B-1) in combination and (B-2) can make the leaching amount of sodium ion and potassium ion be reduced to preferred 2 μ g/cm as component (B) ²Or lower, more preferably 1 μ g/cm ²Or it is lower.

Even when adding to lithium salts (E) in the anti-static resin composition of the present invention, in order further to improve antistatic property, component (B) preferably contains the content reduction of sodium and/or potassium compound (B-1-1) or does not contain the component of this compound (B-1-1).As preferred ingredients (B), can use said components (B-2).By the low component (B) of the content of such use sodium and potassium, the leaching amount of sodium and potassium ion can be reduced to preferred 2 μ g/cm ²Or lower, more preferably 1 μ g/cm ²Or lower, especially preferred undetectable amount.

[0037]

Component of the present invention (C) is to be selected from the segmented copolymer (C-a) that comprises polymer blocks (C-1) and polymer blocks (C-2), with at least a polymkeric substance of its hydrogenated products (C-b) and have elastomer performance, this polymer blocks (C-1) mainly is made up of aromatic vinyl compound, and this polymer blocks (C-2) mainly is made up of conjugated diene compound.

[0038]

Aromatic vinyl compound for example comprises as used herein, vinylbenzene, alpha-methyl styrene and hydroxy styrenes.In the middle of them, vinylbenzene and alpha-methyl styrene are preferred, and vinylbenzene is especially preferred.

Conjugated diene compound comprises, for example, divinyl, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene and 1,3-pentadiene preferably include divinyl and isoprene.They can use individually or two or more use in combination.In addition, block (C-2) can comprise two or more conjugated diene compounds, and they can be by random, block or alternation block form keyed jointing.Block (C-2) can also comprise 1-10 alternation block, wherein the content of aromatic vinyl compound increases gradually, maybe can also be the multipolymer that comprises the different polymer blocks of vinyl bonds content, this vinyl bonds be derived from the conjugated diene compound of polymer blocks (C-2).

[0039]

The preferred construction of component of the present invention (C) is by the polymkeric substance of following general formula (VI)-(VIII) expression or their hydrogenation products.

(A-B) _Y (VI)

(A-B) _Y-X (VII)

A-(B-A) _Z (VIII)

(in general structure (VI)-(VIII), the A representative has the polymer blocks of aromatic vinyl compound as major constituent, and can partly comprise conjugated diene compound, as long as it is the polymer blocks of being made up of aromatic vinyl compound basically.Preferably, A comprises to be no less than 90 quality %, more preferably is no less than the polymer blocks of 99 quality % aromatic vinyl compounds.B represents the homopolymer of conjugated diene compound, or conjugated diene compound and the another kind of monomer multipolymer of aromatic vinyl compound for example.X represents the residue of coupling agent, and Y represents the integer of 1-5, and Z represents the integer of 1-5.When B is conjugated diene compound and another kind of monomer for example during the multipolymer of aromatic vinyl compound, another kind of monomeric content 50 quality % or lower preferably among the B are with respect to this conjugated diene compound and the monomeric total amount of this another kind).

[0040]

The ratio that is ready to use in the aromatic vinyl compound of component of the present invention (C) and conjugated diene compound is preferably at aromatic vinyl compound/conjugated diene compound=10-70/30-90 quality %, 15-65/35-85 quality % further preferably is in the scope of especially preferred 20-60/40-80 quality %.

[0041]

The segmented copolymer that comprises aromatic vinyl compound and conjugated diene compound is known in the technical field of anionoid polymerization, and for example, discloses among Japanese patent application publication No. S47-28915, S47-3252, S48-2423 and the S48-20038.The preparation method of polymer blocks with alternation block discloses among the Japanese patent unexamined publication number S60-81217 for example.

[0042]

Derived from the content of the vinyl bonds (1,2-and 3,4-key) of the conjugated diene compound of component of the present invention (C) preferably in the scope of 5-80%.The number-average molecular weight of component of the present invention (C) preferably 10,000-1,000,000, more preferably 20,000-500,000, especially preferred 20,000-200,000.In the middle of them, the number-average molecular weight of A in general formula (VI)-(VIII) part is preferably 3,000-150, and in 000 the scope, the number-average molecular weight of B part is preferably 5, and 000-200 is in 000 the scope.

[0043]

The adjusting of the vinyl bonds content of conjugated diene compound can use following material to carry out: amine is N for example, N, N ', N-Tetramethyl Ethylene Diamine, Trimethylamine 99, triethylamine, two azo rings (2,2,2) octylame etc., ether is tetrahydrofuran (THF), diethylene glycol dimethyl ether, Diethylene Glycol dibutyl ether etc. for example, thioether, phosphine, phosphamide, alkylbenzene sulfonate, the alkoxide of potassium and sodium etc.

The another kind of preferred examples of component of the present invention (C) comprises by aforesaid method and obtains and have residue prolongation or branched polymers chain via coupling agent with the polymkeric substance of coupling agent treatment so that it.The example of coupling agent comprises diethylene adipate, Vinylstyrene, dimethyl dichlorosilane (DMCS), silicon tetrachloride, butyl trichlorosilicane, tin tetrachloride, butyl tin trichloride, dimethyl chlorination silicon, germanium tetrachloride, 1 as used herein, 2-ethylene dibromide, 1,4-chloromethylbenzene, two (Trichloromonosilane base) ethane, epoxidised Toenol 1140, toluylene group diisocyanate, 1,2,4-benzene triisocyanate etc.

[0044]

In the middle of above-mentioned segmented copolymer, preferably those are the polymkeric substance with block (C-2) for shock-resistance is considered, and/or having experienced the radially block type polymkeric substance of coupling processing, this block (C-2) comprises 1-10 the wherein block that successively decreases that increase gradually of aromatic vinyl compound.

[0045]

In addition, as component (C), the carbon-to-carbon double bond that not only can use above-mentioned segmented copolymer itself but also can use the part of conjugated diolefine wherein partially or completely hydrogenant those.

For consideration to the low temperature shock-resistance of the composition that obtained, preferably use unhydrided those and hydrogenating rate less than 90% those.For consideration to the weathering resistance (photostabilization) of the composition that obtained, preferably use hydrogenating rate be no less than 90% those.

[0046]

Obtain and the hydrogenation that comprises mainly the segmented copolymer of the polymer blocks is made up of aromatic vinyl compound and the main polymer blocks of being made up of conjugated diene compound can be undertaken by known method by aforesaid method.In addition, can regulate hydrogenating rate by known method and obtain required polymkeric substance.Concrete method comprises open (Kokoku) number S42-8704 of Japanese Patent, S43-6636, S63-4841 and S63-5401 and open (Kokai) number H2-133406 of Japanese patent unexamined and H1-297413.

[0047]

Another kind of polymer chemistry can be keyed to above-mentioned segmented copolymer (C-a) and its hydrogenation products (C-b) and go up so that form block polymer and/or graftomer (they can be same or different from the compound as following component (D)).

The above-mentioned another kind of polymkeric substance of 100 (100) percentage not necessarily is chemically bonded on above-mentioned segmented copolymer (C-a) and its hydrogenation products (C-b), and when the above-mentioned another kind of polymer chemistry keyed jointing of at least 10 quality %, purpose of the present invention can realize.

[0048]

Be keyed to above-mentioned another kind of polymkeric substance preferably aromatic polycarbonate and/or urethane on above-mentioned segmented copolymer (C-a) and its hydrogenation products (C-b), further preferred aromatic polycarbonate as block polymer.Can for example pass through, the method for describing among Japanese patent unexamined open (Kokai) number 2001-220506 prepares aromatic polycarbonate segmented copolymer/mixture.In addition, it for example can be used as, Kuraray Co., and the TM-S4L77 and the TM-H4L77 (trade(brand)name) of the TM series of polymers of Ltd. preparation obtain.

[0049]

In addition, the especially preferred method that above-mentioned another kind of polymer graft is aggregated on above-mentioned segmented copolymer (C-a) and its hydrogenation products (C-b) is with the vinyl monomer-grafted polymerization in the presence of above-mentioned segmented copolymer (C-a) and its hydrogenation products (C-b).As vinyl monomer, preferably use the vinyl monomer (D-b) (it can be identical or different with the compound of use in the following component (D)) of component (D).Graft polymerization procedure can be any in the letex polymerization described for component (D) after a while, solution polymerization, mass polymerization, the suspension polymerization etc., and preferably solution polymerization and mass polymerization.

[0050]

In second anti-static resin composition of the present invention, with respect to 100 quality % components (A), (B), (C) and total amount (D), the amount of component (C) is 2-50 quality %, preferred 5-45 quality %, further preferred 7-40 quality %, especially preferred 10-35 quality %.When it during less than 2 quality %, shock-resistance is relatively poor; When it surpassed 50 quality %, shock-resistance and appearance were relatively poor.When said composition as having excellent anti static behaviour and smooth surface and aspect the sheet surface outward appearance during upper layer of outstanding foam layer compressing tablet, the consumption of component (C) is 15-50 quality % preferably, further preferred 20-45 quality % is with respect to 100 quality % components (A), (B), (C) and total amount (D).

[0051]

Component of the present invention (D) is to strengthen styrene resin (D-1) by the rubber that makes vinyl monomer (D-b) the polymerization acquisition that comprises aromatic vinyl compound in the presence of rubbery polymer (D-a), and/or (being total to) polymkeric substance of this vinyl monomer (D-b).It should (being total to) polymkeric substance be compound by vinyl monomer (D-b) polymerization that comprises aromatic vinyl compound is obtained.

For the consideration of impact intensity, preferred component of the present invention (D) comprises at least a polymkeric substance by in the presence of rubbery polymer (D-a) vinyl monomer (D-b) graft polymerization being obtained.The content of rubbery polymer (D-a) is 3-80 quality % preferably, further preferred 5-70 quality %, and especially preferred 10-60 quality %, condition is that component (D) is 100 quality %.

[00S2]

Above-mentioned rubbery polymer (D-a) includes but not limited to polyhutadiene, butadiene-styrene copolymer, perbutan, ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene multipolymer, ethene-1-Butylene copolymer, ethene-butene-1-non-conjugated diene multipolymer, acrylic rubber, silicone rubber, silicone-acrylic resin IPN rubber and said components (C), and they can use individually or two or more use in combination.

In the middle of them, polyhutadiene, butadiene-styrene copolymer, ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene multipolymer, acrylic rubber, silicone rubber and said components (C) are preferred.Butadiene-styrene copolymer can be any in segmented copolymer and the random copolymers as used herein.

[0053]

The gel content of above-mentioned rubbery polymer (D-a) is not particularly limited, but when obtaining component (D-a) by letex polymerization, gel content preferably is no more than 98 quality %, further preferred 40-98 quality %.In this scope, can obtain to produce the especially anti-static resin composition of the multi-layer sheet of excellence aspect shock-resistance.

Above-mentioned gel content can be measured by the following method.That is, the 1g rubbery polymer is added in the 100ml toluene, and allow this mixture at room temperature to leave standstill 48 hours.(quality definition is W to allow this mixture filter 100 order metal screens then ₁And weigh that (quality definition is W gram), and this filtering toluene insoluble material of 80 ℃ of following vacuum-dryings and metal screen 6 hours, ₂Gram).Gel content calculates by following formula (1).

[0054]

Gel content (quality %)=[{ W ₂(g)-W ₁(g) }/1 (g)] * 100... (1)

By during the preparation of rubbery polymer, suitably adjusting the kind and the consumption of molecular weight improving agent, polymerization time, polymerization temperature, adjusting such as polymerisation conversion gel content.

[0055]

The aromatic vinyl compound that constitutes above-mentioned vinyl monomer (D-b) comprises vinylbenzene, alpha-methyl styrene, hydroxy styrenes etc.They can use individually or two or more use in combination.In the middle of them, vinylbenzene and alpha-methyl styrene are preferred.

[0056]

Can for example comprise that vinyl cyanide compound, (methyl) acrylic compound, maleimide compound and various other contain the unsaturated compound of functional group with other vinyl monomer of aromatic vinyl compound copolymerization.Vinyl monomer (D-b) preferably comprises aromatic vinyl compound as the basic monomer component, and comprise if necessary be selected from vinyl cyanide compound, (methyl) acrylic compound and the maleimide compound one or both or more kinds of as additional monomer component, if and further necessary, comprise described various other and contain at least a in the unsaturated compound of functional group as additional monomer component.The described various unsaturated compound that other contains functional group for example comprises, the unsaturated compound of unsaturated acid compound, the unsaturated compound that contains epoxy group(ing), hydroxyl, contain azoles quinoline base unsaturated compound, contain the unsaturated compound of anhydride group and contain and replace or the unsaturated compound of unsubstituted amino.

The described various unsaturated compound that other contains functional group can use individually or two or more use in combination.

[0057]

Vinyl cyanide compound for example comprises as used herein, vinyl cyanide and methacrylonitrile, and they can use individually or two or more use in combination.When using vinyl cyanide compound, give chemical-resistant.When using vinyl cyanide compound, its amount to be used is with respect to component (D-b) preferably 1-60 quality %, more preferably 5-50 quality %.

(methyl) acrylic compound for example comprises, methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi and butyl methacrylate, and they can use individually or two or more use in combination.

The use of (methyl) acrylic compound improves surface hardness, and is preferred therefore.When using (methyl) acrylic compound, its amount to be used is with respect to component (D-b) preferably 1-80 quality %, more preferably 5-80 quality %.

Maleimide compound comprises, for example, maleimide, N-phenylmaleimide and N-cyclohexyl maleimide, and they can use individually or two or more use in combination.In order to introduce the maleimide amine unit,, can carry out imidization then at first with the maleic anhydride copolymerization.When using maleimide compound, give thermotolerance.When using maleimide compound, its amount to be used is with respect to component (D-b) preferably 1-60 quality %, more preferably 5-50 quality %.

[0058]

The unsaturated acid compound for example comprises, vinylformic acid, methacrylic acid, ethylacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid, Ba Dousuan and styracin, and they can use individually or two or more use in combination.

The unsaturated compound that contains epoxy group(ing) comprises, for example, glycidyl acrylate, glycidyl methacrylate and glycidyl allyl ether, and they can use individually or two or more use in combination.

[0059]

The unsaturated compound of hydroxyl for example comprises, 3-hydroxyl-1-propylene, 4-hydroxyl-1-butylene, cis-4-hydroxyl-2-butylene, trans-4-hydroxyl-2-butylene, 3-hydroxy-2-methyl-1-propylene, methacrylic acid 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxyl ethyl ester and N-(4-hydroxyphenyl) maleimide, and they can use individually or two or more use in combination.

The unsaturated compound of Han oxazolinyl comprises, for example, Yi Xi oxazolin, and they can use individually or two or more use in combination.

The unsaturated compound that contains anhydride group for example comprises, maleic anhydride, itaconic anhydride and citraconic anhydride, and they can use individually or two or more use in combination.

The unsaturated compound that contains replacement or unsubstituted amino for example comprises; vinylformic acid ammonia ethyl ester, vinylformic acid propyl group ammonia ethyl ester, dimethylaminoethyl acrylate methyl base ammonia ethyl ester, methacrylic acid phenylamino ethyl ester, N-vinyl diethylamine, N-ethanoyl vinyl-amine, acryl amine, methacryloyl amine, N-methacryloyl amine, acrylamide, N methacrylamide and p-aminophenyl ethene, and they can use individually or two or more use in combination.

When using the described various unsaturated compound that contains other functional group, can expect that the blend of styrene resin and another kind of polymkeric substance will be improved aspect the two the consistency.The preferred monomer that reaches a kind of like this effect is the unsaturated compound of the unsaturated compound, unsaturated acid compound and the hydroxyl that contain epoxy group(ing).

The above-mentioned various to be used amount of unsaturated compound in component (D) that contains other functional group is with respect to component (D) 0.1-20 quality % preferably, and more preferably 0.1-10 quality % contains the total amount of the unsaturated compound of functional group by these.

[0060]

Amount monomeric to be used in the vinyl monomer (D-b) except that aromatic vinyl compound is 10-95 quality % preferably, more preferably 10-90 quality %, and especially preferred 15-80 quality %, condition is that the total amount of vinyl monomer (D-b) is 100 quality %.The monomeric more preferably combination that constitutes vinyl monomer (D-b) for example comprises, styrene/acrylonitrile, styrene/methacrylic acid methyl esters, styrene/acrylonitrile/methyl methacrylate, styrene/acrylonitrile/glycidyl methacrylate, styrene/acrylonitrile/methacrylic acid 2-hydroxyl ethyl ester, styrene/acrylonitrile/(methyl) vinylformic acid, vinylbenzene/N-phenylmaleimide and styrene/methacrylic acid methyl esters/cyclohexyl maleimide, especially preferred combination is a styrene/acrylonitrile.Treat that the monomeric more preferably combination of polymeric comprises styrene/acrylonitrile=65/45-90/10 (mass ratio), styrene/methacrylic acid methyl esters=80/20-20/80 (mass ratio) and styrene/acrylonitrile/methyl methacrylate in the presence of rubbery polymer (D-a), wherein cinnamic amount is 20-80 quality %, the amount of the summation of vinyl cyanide and methyl methacrylate is 20-80 quality %, and especially preferred combination is styrene/acrylonitrile=70/30-85/15 (mass ratio).

[0061]

Component of the present invention (D) can be by the polymerization process preparation of for example letex polymerization of known polymerization process, mass polymerization, solution polymerization, suspension polymerization and their combination.In the middle of them, be letex polymerization and solution polymerization by the preferred polymerization process that in the presence of rubbery polymer (D-a), makes the polymkeric substance that vinyl monomer (D-b) (being total to) polymerization obtains.On the other hand, be mass polymerization, solution polymerization, suspension polymerization and letex polymerization by the preferred polymerization process that under the situation that does not have rubbery polymer (D-a), makes the polymkeric substance that vinyl monomer (D-b) (being total to) polymerization obtains.

[0062]

When producing by letex polymerization, use polymerization starter, chain-transfer agent, emulsifying agent etc., and all these can be usually known those.

Polymerization starter for example comprises that cumene hydroperoxide, hydroperoxidation are to menthane, hydroperoxidation diisopropyl benzene, hydroperoxidation tetramethyl butyl, t-butyl hydroperoxide, Potassium Persulphate and Diisopropyl azodicarboxylate.

In addition, cause auxiliary agent, preferably use for example various reductive agents of redox system, contain sugared ferric pyrophosphate prescription and sulfoxylate prescription as polymerization.

Chain-transfer agent comprises that for example, mercaptan is octyl mercaptan, n-dodecyl mercaptan, uncle's lauryl mercaptan, n-hexyl mercaptan, terpinolene and alpha-methyl styrene dimer for example.

Emulsifying agent comprises that for example, alkylbenzene sulfonate is Sodium dodecylbenzene sulfonate for example, and aliphatic sulfonate is Sodium Lauryl Sulphate BP/USP for example, and higher fatty acid salt is potassium laurate, potassium stearate, potassium oleate and potassium palmitate and sylvate resin acid potassium for example for example.

[0063]

As for the mode that rubbery polymer (D-a) and vinyl monomer (D-b) is used for letex polymerization, can fully add vinyl monomer (D-b) and polymerization in the presence of total amount rubbery polymer (D-a), or can be dividually or add continuously and polymerization.In addition, can in polymerization process, add a part of rubbery polymer (D-a).

[0064]

After letex polymerization, the latex and the condensing agent that are obtained are condensed, wash with water also dry then and the powder of acquisition component of the present invention (D).During this time, two or more latex blend of the component (D) that can be suitably will obtain by letex polymerization are condensed then.Condensing agent 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 as used herein.

[0065]

Operable solvent is that they are used for common radical polymerization to polymerization inert solvent when by solution polymerization component (D).Their 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 80-140 ℃, more preferably 85-120 ℃.

Between polymerization period, can use polymerization starter, perhaps can under the situation of not using polymerization starter, carry out polymerization by thermopolymerization.The preferred polymerization starter that uses for example comprises, organo-peroxide for example ketone peroxide, dialkyl, peroxidation two acyls, peroxyester, hydroperoxide, Diisopropyl azodicarboxylate, benzoyl peroxide and 1,1 '-azo two (hexanaphthene-1-nitrile).

In addition, when using chain-transfer agent, it for example can be, mercaptan, terpenolenes and α-Jia Jibenyixierjuwu.

When producing, can use the polymerization starter that relates to solution polymerization and describe, chain-transfer agent etc. by mass polymerization or suspension polymerization.

Preferably be no more than 10 by remaining monomeric amount in the component (D) of above-mentioned corresponding polymerization process acquisition, 000ppm further preferably is no more than 5,000ppm.

[0066]

Generally include wherein by the polymeric constituent that in the presence of rubbery polymer (D-a) vinyl monomer (D-b) polymerization is obtained that this vinyl monomer (D-b) graft copolymerization is incorporated into the multipolymer on this rubbery polymer (D-a) and does not have the grafted component, this does not have the grafted component to be made by this vinyl monomer (D-b) but is not grafted to ((being total to) polymkeric substance of above-mentioned vinyl monomer (D-b)) on this rubbery polymer.

The percentage of grafting of said components (D) is 20-200 quality % preferably, further preferred 30-150 quality %, and especially preferred 40-120 quality %, and this percentage of grafting can be measured by following formula (2).

[0067]

Percentage of grafting (quality %)=(T-S)/S} * 100.. (2)

In the above-mentioned formula (2), T is the quality (g) of the insoluble substance of following acquisition: add 1g component (D) to 20ml acetone (when using acrylic rubber in rubbery polymer (D-a), but acetonitrile) in, shook this mixture 2 hours by wobbler, pass through whizzer then (with 23, the rotating speed of 000rpm) this mixture of centrifugation 60 minutes is with separatin non-soluble material and soluble substance, and S is the quality (g) of the rubbery polymer that comprises in the 1g component (D).

[0068]

The soluble substance of component of the present invention (D) at acetone (when in rubbery polymer (a), using acrylic rubber, but acetonitrile) limiting viscosity in [η] (using methyl ethyl ketone to measure down at 30 ℃ as solvent) is 0.2-1.2dl/g preferably, further preferred 0.2-1.0dl/g, especially preferred 0.3-0.8dl/g.

The median size that is dispersed in the grafted rubber-like polymer particle in the component (D) is 500-30 preferably, and 000 dust is further preferred 1,000-20, and 000 dust, especially preferred 1,500-8,000 dust.Can use electron microscope to measure median size by ordinary method.

[0069]

The amount to be used of component (D) is 5-50 quality % in the present invention's second anti-static resin composition, preferred 7-50 quality %, further preferred 7-38 quality %, especially preferred 10-30 quality % is with respect to 100 quality % components (A), (B), (C) and total amount (D).When this measured less than 5 quality %, static resistance, shock-resistance and molded article surface outward appearance were relatively poor; When it surpasses 50 quality %, static resistance and chemical-resistant are relatively poor.When said composition as having excellent anti static behaviour and smooth surface and aspect the sheet surface outward appearance during upper layer of outstanding foam layer compressing tablet, the amount to be used of component (D) is 5-20 quality % preferably, further preferred 5-15 quality % is with respect to 100 quality % components (A), (B), (C) and total amount (D).

[0070]

In order further to improve antistatic property, can in the production process of anti-static resin composition of the present invention, lithium salts (E) and/or non-ionic antistatic agent (F) be added in this anti-static resin composition.

[0071]

As lithium salts (E), can use above-mentioned any component (E), and they can use individually or two or more use in combination.With respect to 100 mass parts anti-static resin composition of the present invention, lithium salts (E) is preferably with the 0.01-5 mass parts, further preferred 0.1-3 mass parts, and especially preferred 0.3-2 mass parts is used.When its amount to be used during less than 0.01 mass parts, be unreachable to the improvement effect of antistatic property, when it surpassed 5 mass parts, shock-resistance often reduced.

[0072]

When lithium salts (E) blend in the present invention's second anti-static resin composition the time, is provided to satisfy to have 1 * 10 ¹¹Ω/ or lower, preferred 1 * 10 ⁹Ω/ or lower surface resistivity (under the condition of 23 ℃ and 50%R.H., measuring) and 3 μ g/cm ²Or lower, the moulded product of the requirement condition of sodium that preferably can not detection limit and potassium ion leaching amount (under the condition of 80 ℃ and extraction in 60 minutes, measuring), thus antistatic property and ion are equilibrated to than higher in the past degree between leaching.In ordinary method, the blending amount that increases said components (B) to be improving antistatic property, but in this case, often leaches from the ion of moulded product and improves.On the contrary, according to the present invention, lithium salts that can be by the blend predetermined amount and the preferred low or compound that is substantially free of these elements of sodium and/or potassium content that uses can obtain antistatic property and ion and leach highly equilibrated moulded product as said components (B).

[0073]

Non-ionic antistatic agent (F) for example comprises, polyol ester, amine and acid amides.The example of polyol ester for example comprises, glyceryl monostearate, single myristin, monopalmitin, glyceryl monostearate Dan docosoic glyceryl ester, XU 61518.10, mono laurate two glyceryl ester, single myristic acid two glyceryl ester, single palmitinic acid two glyceryl ester, Stearinsaeure two glyceryl ester Dan docosoics two glyceryl ester, single oleic acid two glyceryl ester, the mono laurate Isosorbide Dinitrate, single myristic acid Isosorbide Dinitrate, single palmitinic acid Isosorbide Dinitrate, Stearinsaeure Isosorbide Dinitrate Dan docosoic Isosorbide Dinitrate and mono laurate Isosorbide Dinitrate, and they can use individually or two or more use in combination.Especially preferred is glyceryl monostearate, Stearinsaeure two glyceryl ester, glyceryl monolaurate, mono laurate two glyceryl ester, Stearinsaeure Isosorbide Dinitrate and the material that comprises at least 20 these materials of quality %.

[0074]

Amine and acid amides comprise, for example, amine compound is the lauryl diethanolamine for example, the myristyl diethanolamine, the palmityl diethanolamine, octadecyldiethanol amine, the oleyl diethanolamine, the lauryl diisopropanolamine (DIPA), the myristyl diisopropanolamine (DIPA), the palmityl diisopropanolamine (DIPA), the octadecyl diisopropanolamine (DIPA), oleyl diisopropanolamine (DIPA) and N, two hydroxyethyl alkylamines (its alkyl contains 12-22 carbon atom) of N-and amide compound be the lauryl diglycollic amide for example, the myristyl diglycollic amide, the palmityl diglycollic amide, the docosyl diglycollic amide, the oleyl diglycollic amide, lauryl diisopropanol acid amides, myristyl diisopropanol acid amides, palmityl diisopropanol acid amides, octadecyl diisopropanol acid amides and oleyl diisopropanol acid amides.

They can use individually or two or more use in combination.Preferred what use is above-mentioned amine compound, further preferably comprises in 20 quality % lauryl diethanolamine and the octadecyldiethanol amine material of each at least.

[0075]

In order to improve the static resistance of above-claimed cpd, can the blend conventional additives.Their example comprises the higher alcohols that contains 12-18 carbon atom, lubricant, silicon-dioxide and Calucium Silicate powder.In order to improve miscibility, can use those that make masterbatch.

Above-mentioned non-ionic antistatic agent is commercially available, comprises ELECTROSTRIPPER EA, TS-3B, TS-6B, TS-5, TS-2B (trade(brand)name) by Kao Corporation preparation.

[0076]

With respect to 100 mass parts anti-static resin composition of the present invention, above-mentioned non-ionic antistatic agent is preferably with the 0.01-10 mass parts, further preferred 0.1-8 mass parts, and especially preferred 0.1-5 mass parts is used.

When its amount to be used during less than 0.01 mass parts, be unreachable to the improvement effect of static resistance, when it surpassed 10 mass parts, the appearance of moulded product was easy to reduce.

[0077]

In anti-static resin composition of the present invention, suitably conventional weather (light) agent of blend, antioxidant, thermo-stabilizer, antiseize paste, silicone oil, softening agent, lubricant, tinting material, dyestuff, whipping agent, processing aid (ultra-high molecular weight acrylic acid polymer and ultra high molecular weight phenylethylene polymkeric substance), fire retardant and crystal nucleation additive etc.

In addition, known inorganic or organic filler can with anti-static resin composition blend of the present invention.Filler for example comprises as used herein, glass fibre, glass flake, the milled fibre of glass fibre, glass powder, granulated glass sphere, Hollow Glass Sphere, carbon fiber, the milled fibre of carbon fiber, for example silver-colored, copper, the powder of brass and iron or filamentary material, carbon black, zinc-plated titanium oxide, zinc-plated silicon-dioxide, nickel-coated carbon fibers, talcum, lime carbonate, calcium carbonate crystal whisker, wollastonite, mica, kaolin, polynite, hectolite, ZnOw, potassium titanate crystal whisker, aluminium borate whisker, piece aluminum oxide, sheet silicon-dioxide and organically-modified terre verte, Kevlar, resol and trevira, and they can use individually or two or more use in combination.In addition,, can use those that handle with known coupling agent, surface treatment agent, sizing agent etc., and known coupling agent comprises in order to improve the dispersibility of filler, for example, silane coupling agent, titanate coupling agent and aluminum coupling agent.

With respect to 100 mass parts anti-static resin composition of the present invention, above-mentioned inorganic or organic filler is generally used with the 1-200 mass parts.

[0078]

In addition, anti-static resin composition of the present invention can be suitably and other known polymer blending, for example polyamide resin, polyamide elastomer, polybutylene terephthalate, polyethylene terephthalate, polyarylester, thermoplastic polyester is liquid crystal polyester for example, polyester elastomer, PMMA, the multipolymer of methyl methacrylate and maleimide compound, polyphenylene oxide, polyphenylene sulfide, aromatic polycarbonate, thermoplastic polyurethane, the multipolymer of ethene and (methyl) methyl acrylate, ethene and (methyl) acrylic acid multipolymer, Resins, epoxy, phenol resins, urea resin and phenoxy resin.

[0079]

Can be by obtaining anti-static resin composition of the present invention with melt kneading said components such as various forcing machines, Banbury blender, kneading machine, continuous kneading machine, rollers.

During mediating, can be with the whole chargings of corresponding component mediating, or the portioning charging is to mediate.So the anti-static resin composition of preparation can be by for example injection moulding of conventional moulding method, pressing mold, rolling press molding, T-mould extrusion molding, blow moulding, lamination molding, vacuum moulding and special-shaped extrusion molding in the present invention, and moulded product is made in the combination of these moulding method.In addition, when the mould machine that for example is used to roll molding, T-mould extrusion molding and blow moulding is equipped with kneading machine for example when kneading extruder and Banbury blender, can when preparing anti-static resin composition of the present invention, obtain moulded product, and not need to obtain in advance anti-static resin composition of the present invention by the kneading machine of installing.

[0080]

When anti-static resin composition of the present invention was processed into sheet material or film, thickness is 10 μ m-100mm preferably.

Above-mentioned sheet material and film can be single layer articles, maybe can be and the laminated multi-layer product of other material.In addition, they can be that pressure sensitive adhesive etc. is in turn laminated to sheet material and the film on it.In addition, can arrive formation conventional gas barrier films on this sheet material and the film.

[0081]

When using anti-static resin composition of the present invention to form multi-layer sheet or multilayer film, anti-static resin composition of the present invention can form, for example, have the double layer sheet or the film of another kind of material or have three-layer tablet material or the film of another kind of material as sandwich layer.The material that another kind of as used herein material can be made up of known polymkeric substance.This kind multi-layer sheet or multilayer film are preferred embodiment of the invention, because the use of component of the present invention (A), component (D) etc. provides excellent layer-to-layer adhesion.When using the inadequate material of layer-to-layer adhesion, known tackiness agent can be inserted between them.In addition, for rigidity and the thermotolerance of improving sheet material and film, also can use and material inorganic or the organic filler blend.

In above-mentioned multi-layer sheet, the thickness 10 μ m or higher preferably of the layer of making by anti-static resin composition of the present invention, further preferred 50 μ m or higher, especially preferred 80 μ m or higher are so that stably show antistatic property.The preferred method that obtains multi-layer sheet and film is to use the coextrusion method of T-mould and the coextrusion method of use inflation.In case of necessity, the sheet material that so obtains can be made for example plate of moulded product by vacuum moulding etc.

[0082]

When use comprises that the multi-layer sheet of the layer of anti-static resin composition of the present invention and other layer of acrylic resin or sandwich layer carries out vacuum moulding, the acrylic resin that is used for other layer or sandwich layer preferably melt flow rate (MFR) (adopting the load measurement of 2.16kg according to JIS K7210:1999 under 230 ℃ temperature) is 1.0g/10min or lower acrylic resin, is the acrylic resin that 1.0g/10min or lower polyethylene combine with 10-30% melt flow rate (MFR) (adopting the load measurement of 2.16kg according to JIS K6922-2 under 190 ℃ temperature) preferably further.

[0083]

When the sheet material that uses anti-static resin composition of the present invention or film during as substrate preparation pressure-sensitive adhesive sheets or film, the sheet material of anti-static resin composition of the present invention or the surface of film can experience known various processing, Corona discharge Treatment, flame treating, oxide treatment, plasma treatment, UV are handled, ion bombardment processing or solvent treatment, to improve to the adhesion of this pressure sensitive adhesive or to the adhesion of prime coat.

In addition, for the sheet material that improves pressure sensitive adhesive and anti-static resin composition of the present invention or the bond strength between the film, can be directly on the surface of the sheet material of anti-static resin composition of the present invention or film or on the surface that experiences above-mentioned processing, form prime coat.Especially, for example polymine, urethane and acrylic resin form extremely thin layer of the about 0.1 μ m-10 μ m of thickness on above-mentioned surface to use resin.Usually, can be by applying solvent (comprising water) solution then with its dry this layer that forms.

[0084]

Pressure sensitive adhesive comprises, for example, adopt silk screen method, notch board method, screen cloth method, excellent cladding process etc. to apply and the emulsion-type and the organic solvent type of formation binder layer, and adopt and extrude the hot-melting type that laminating method, dried laminating method, coextrusion method etc. form binder layer, and can use any of these.In addition, the thickness of pressure sensitive adhesive is not particularly limited, but is typically about about 1-100 μ m.

The structure of each of multi-layer sheet of the present invention layer is not particularly limited, but can be, for example, and foam or hollow.When the layer that will be made by above-mentioned another kind of material, for example, by when foaming layer that said components (A) is made, whipping agent is not particularly limited, but for example can be, is used for the known whipping agent of foam polypropylene resin or foamed polyethylene resin.The specific examples of whipping agent comprises inorganic pore forming material for example carbonic acid gas, air and nitrogen, but volatile foaming agent for example Cellmic C 121 (ADCA), dinitrosopentamethylene tetramine, azobis isobutyronitrile, hydrazo-dicarbonamide and sodium bicarbonate of aliphatic hydrocrbon, halohydrocarbon and decomposition-type foaming agent for example.They can use individually or two or more use in combination.In the middle of them, but preferred what use is decomposition-type foaming agent, because can easily regulate molding temperature and foam volume.In addition, the amount to be used of whipping agent is not particularly limited, but but under the situation of decomposition-type foaming agent, being used for foam moulded resin combination with respect to 100 mass parts, this measures preferably 0.1-10 mass parts.

When first anti-static resin composition of the present invention is used as the upper layer of above-mentioned foam article, can compatibly use and comprise 40-80 quality % olefin resin (A) and 20-60 quality % segmented copolymer (B) (condition is that said components (A) and total amount (B) are 100 quality %), and the composition that randomly comprises 0.01-5 mass parts lithium salts (E) is with respect to 100 mass parts said components (A) and total amounts (B).In addition, when second anti-static resin composition of the present invention is used as the upper layer of above-mentioned foam article, can compatibly use and comprise 7-30 quality % olefin resin (A), 20-60 quality % segmented copolymer (B), 15-50 quality % elastomerics (C) and 5-20 quality % styrene resin (D) (condition is that said components (A), (B), (C) and total amount (D) are 100 quality %), and randomly comprise the composition of 0.01-5 mass parts lithium salts (E), with respect to 100 mass parts said components (A), (B), (C) and total amount (D).

[0085]

So the moulded product that obtains can be used for, and for example, the box field is interconnecting device, wafer case, netting twine box and shielding box for example; Plate for example liquid crystal panel, chip disk, hard disk (HDD), CCD dish, IC dish, organic EL dish, light obtains relevant dish, LED dish and memory disc; Carrier is the IC carrier for example; The protective film of polarization film, light guiding plate and various lens for example; The protectiveness sheet material that when cutting off polarization film, uses; Be used for for example dividing plate of the sheet material of cleaning chamber or film; The internals of vending machine; The antistatic bag that is used for liquid crystal panel, hard disk and plasma panel; The plastics clamp; Be used for the soft box that liquid crystal panel, plasma panel etc. are carried; And other member relevant with the conveying that is used for various parts.

Embodiment

[0086]

To the present invention be described in more detail via embodiment below.Yet the present invention is in no way limited to these embodiment, unless it breaks away from the scope of the invention really.The ＂ of unit part ＂ among the embodiment and ＂ % ＂ are based on quality, unless otherwise prescribed.In addition, the various measurements among embodiment and the comparative example are based on following method.

[0087]

1. evaluation method

(1) gel content of rubbery polymer;

Measure according to aforesaid method.

(2) median size of rubbery polymer latex;

The median size that is used to prepare the rubbery polymer latex of component (D-1) is measured by light scattering method.Use LPA-3100 (by Otsuka Electronics Co., Ltd. makes) to measure according to semi-invariant method (70 multiplicatrix branch) as measuring engine.The graft rubber shaped polymer particulate particle size that is dispersed in the component (D) adopts electron microscope to confirm as almost identical with latex particle.

(3) percentage of grafting of component (D);

Measure according to aforesaid method.

(4) limiting viscosity [η] of the acetone soluble material of component (D);

Measure according to aforesaid method.

(5) component (C) (the keyed jointing styrene content of polymkeric substance, vinyl bonds content, number-average molecular weight and hydrogenating rate);

(5-1) keyed jointing styrene content; The polymer measurement of use before hydrogenation.

By the working curve that obtains by infrared research based on phenyl at 699cm ^-1The specific absorption at place is measured.

(5-2) number-average molecular weight;

The polymer measurement of use before hydrogenation.

Measure by gel permeation chromatography (GPC).

(5-3) vinyl bonds content;

The polymer measurement of use before hydrogenation.Measure by infrared research (Morello method).

(5-4) hydrogenating rate;

The polymer measurement of use after hydrogenation.By at 100MHz ¹The spectrum of unsaturated double-bond reduces calculating, this 100MHz in the H-NMR spectrum ¹H-NMR spectrum is measured under 15% concentration of use zellon as solvent.

[0088]

(6) static resistance;

(6-1) static resistance-1

According to using by United States ETS, Ltd. the FTMS-101 of the STATIC DECAY METER406D of Zhi Zaoing (United States Federal Test Standard), will+5 under the condition of the moisture of 23 ℃ temperature and 12%RH, 000V be applied to moulded product (on size: 2.4mm * 76mm * 127mm), then with this moulded product ground connection to measure up to the time (second) of voltage attenuation to 50V.

(6-2) static resistance-2

Use the HIRESTA-UP MCPHT450 for preparing by MITSUBISHI CHEMICAL Corporation. according to JISK6911, allowing moulded product leaves standstill 24 hours under the humidity condition of 23 ℃ temperature and 50%R.H. after, measure this moulded product (size: 2.1mm * 100mm Disk) surface resistivity (Ω/).

(7) chemical-resistant;

1% strain is applied to moulded product (on size: 2mm * 40mm * 160mm), and to apply dioctyl phthalate (DOP) (DOP) thereon.Allow this moulded product under 23 ℃, leave standstill then 72 hours.Then, visually estimate the surface condition of this moulded product according to following judgement criteria.

Zero; No change.

△; Small cracking.

*; Cracking largely or fragmentation

(8) appearance

Visually estimate moulded product (size: 2.1mm * 100mm according to following judgement criteria Disk) the surface.

◎; Surface smoothing, and outward appearance is very good.

Zero; Surface smoothing, and outward appearance is good.

△; The surface is inhomogeneity slightly, but in fact outward appearance can be accepted.

*; The surface is inhomogeneous, and appearance poor.

(9) shock-resistance;

(9-1) shock-resistance-1

According to ISO 179, measure Charpy shock strength (KJ/m by the predetermined moulded product of identical ISO ²).

(9-2) shock-resistance-2

According to ASTM-D2794, measurement mode goods (the Dupont shock strength (kgfcm) of size: 2.4mm * 100mm * 100mm).

(10) ionic leaching amount;

To have 88cm ²The moulded product of surface-area is dipped in 88cm ³In the ultrapure water under 80 ℃, from this moulded product, to leach ion 60 minutes.Adopt the sodium ion of this extraction water of ion chromatography measurement and the total amount of potassium ion.This result is changed into the value of per unit area moulded product and uses μ g/cm ²Expression.

(11) thermostability;

The similar moulded product of moulded product that transference above-mentioned static resistance-1 is measured leaves standstill 5 days in 90 ℃ atmosphere after with before visually estimate the colour-change of this moulded product according to following judgement criteria.

Zero; No change or subtle change.

*; Noticeable change.

[0089]

2. the component of anti-static resin composition

(1) component (A); Olefin resin

Following olefin resin is as component of the present invention (A).

A1; NOVATEC PPFY6C (trade(brand)name) by Japan Polypropylene Corporation manufacturing: homopolymerization type polypropylene, melt flow rate (MFR) 2.4g/10min.

A2; NOVATEC PPMA3AH (trade(brand)name) by Japan Polypropylene Corporation manufacturing: homopolymerization type polypropylene, melt flow rate (MFR) 10g/10min.

A3; NOVATEC PPEG6D (trade(brand)name) by Japan Polypropylene Corporation manufacturing: random polypropylene, melt flow rate (MFR) 1.9g/10min.

A4; NOVATEC PPMG3ATB (trade(brand)name) by Japan Polypropylene Corporation manufacturing: random polypropylene, melt flow rate (MFR) 10g/10min.

A5; NOVATEC PPEA9BT (trade(brand)name) by Japan Polypropylene Corporation manufacturing: homopolymerization type polypropylene, melt flow rate (MFR) 0.5g/10min.

A6; HARMOREXNF464N (trade(brand)name) by Japan Polyethylene Corporation manufacturing: metallocene polyethylene, melt flow rate (MFR) 2.0g/10min.

A7; NOVATEC LDLF122 (trade(brand)name) by Japan Polyethylene Corporation manufacturing: new LDPE (film grade), melt flow rate (MFR) 0.3g/10min.

A8; TOPAS 8007X10 (trade(brand)name) ethylene-norbornene copolymer (second-order transition temperature by Japan Polyplastics Corporation manufacturing; 80 ℃).

A9; NOVATEC HDHB530 (trade(brand)name) by Japan Polyethylene Corporation manufacturing: high density polyethylene(HDPE), melt flow rate (MFR) 0.3g/10min.

A10; NOVATEC LDHJ560 (trade(brand)name) by Japan Polyethylene Corporation manufacturing: high density polyethylene(HDPE), melt flow rate (MFR) 7g/10min.

[0090]

(2) component (B)

(2-1) component (B-1)

(2-1-1) preparation embodiment 1; The polypropylene of compounds containing sodium-polyoxyethylene glycol block altogether Polymers

Put into the autoclave by stainless steel made by the thermal destruction method by the low-molecular-weight polypropylene (Mn=2,500) that high molecular weight polypropylene obtains with 80 parts.Under 160 ℃, make its fusion then, and to wherein adding 7 parts of maleic anhydrides and 14 parts of 12 amino dodecanoic acids.Under nitrogen gas stream, allow this mixture under agitator, to react one hour down at 160 ℃.Then, under 200 ℃, reacted 20 hours, and obtain polyolefin block (B-a).(B-a) acid number is 32.1, and its Mn is 2,800.

With 64 parts above-mentioned (B-a), 36 parts of polyoxyethylene glycol (Mn=2,000), 8 parts of Sodium dodecylbenzene sulfonatees, 0.3 part of Ciba-Geigy Corporation antioxidant IRGANOX1010 (trade(brand)name) and 0.5 part of zirconyl acetate of making add in the autoclave of being made by stainless steel, and carried out polymerization 4 hours and the acquisition sodium content is the polymkeric substance of 4000ppm under 230 ℃ and 1mmHg or lower reduced pressure.Take out this polymkeric substance and granulation with the belt form and obtain segmented copolymer (B1-1).The Mn of this segmented copolymer (B1-1) is 25,000.In addition, the average repeat number of this segmented copolymer (B1-1) is 5.0, by this Mn and ¹The H-NMR assay determination.

(2-1-2) preparation embodiment 2; The polypropylene of potassium-containing compound-polyoxyethylene glycol block altogether Polymers

Obtain to have the segmented copolymer (B1-2) of potassium content 4000ppm with the method the same with preparing embodiment 1, difference is to use 0.75 part of Repone K to replace Sodium dodecylbenzene sulfonate.

(2-1-3) preparation embodiment 3; The polypropylene of compounds containing sodium-polyoxyethylene glycol block altogether Polymers

Obtain to have the segmented copolymer (B1-3) of sodium content 2000ppm with the method the same with preparing embodiment 1, difference is the amount to be used of Sodium dodecylbenzene sulfonate is changed to 3.9 parts.

(2-2) component (B-2)

(2-2-1) preparation embodiment 4; Polypropylene-polyethyleneglycol block copolymer

By obtaining the not segmented copolymer of compounds containing sodium (B2-1) with preparation embodiment 1 similar mode, difference is not use Sodium dodecylbenzene sulfonate.

[0091]

(3) component (C)

(3-1) preparation embodiment 5; Styrene butadiene is the teleblock multipolymer radially

Drying is equipped with the chuck autoclave of agitator and uses nitrogen purging.Under nitrogen gas stream, to wherein adding hexanaphthene and 2.75 parts of tetrahydrofuran (THF)s.Replenish this mixture with 25 parts of vinylbenzene, and with temperature increase to 60 ℃.Replenish this mixture, 60 minutes (fs) of polymerization gained mixture then with the cyclohexane solution that contains 0.175 part of n-Butyl Lithium then.Next, add by 3 parts of vinylbenzene and 20 parts of mixtures that divinyl constitutes, and the mixture of polymerization gained 60 minutes (subordinate phase).Next add by 3 parts of vinylbenzene and 20 parts of mixtures that divinyl constitutes, and 60 minutes (phase III) of the mixture of polymerization gained.Next, add 29 parts of divinyl, and carry out polymerization up to reaching 100% transformation efficiency.With the mixture of 0.1 part of silicon tetrachloride, finish coupled reaction then as the additional gained of coupling agent.After polymerization was finished, with respect to 100 parts of multipolymers that obtain above, with 0.3 part 2,6-two-tert-butyl catechol replenished this polymers soln, remove then and desolvate, and acquisition has the coupling type styrene-butadiene block copolymer C1 of the block that successively decreases.

This multipolymer has 31% styrene content and 200,000 number-average molecular weight.

[0092]

(3-2) preparation embodiment 6; Hydrogenant styrene-butadiene-styrene block altogether fully Polymers

Drying is equipped with the autoclave of agitator and chuck and uses nitrogen purging, and will contain 30 parts of cinnamic cyclohexane solutions and be placed on wherein.

Then, add n-Butyl Lithium, and under 70 ℃, carry out after the polymerization 1 hour, add and contain the cyclohexane solution of 40 parts of divinyl to carry out polymerization 1 hour.In addition, interpolation contains 30 parts of cinnamic cyclohexane solutions to carry out polymerization 1 hour.The block polymer solution that a sampling part is obtained, and with respect to 0.3 part 2 of 100 parts of segmented copolymers interpolation, 6-two-tert-butyl pyrocatechol is then by adding the heat extraction solvent.This material have 60% styrene content and in the polyhutadiene part 35% 1,2-contents of ethylene, and have 74,000 number-average molecular weight.To add in the remaining block copolymer solution by the solution that cyclopentadienyl titanium dichloride and triethyl aluminum is reacted obtain in hexanaphthene, and under 50 ℃ at 50kgf/cm ²Hydrogen pressure under carried out hydrogenation 3 hours.Add 0.3 part 2 with respect to 100 parts of segmented copolymers, 6-two-tert-butyl catechol obtains polymkeric substance C2 then except that desolvating, and wherein the hydrogenating rate of divinyl part is 100%.

[0093]

(4) component (D)

(4-1) preparation embodiment 7; ABS resin

Under nitrogen gas stream, place 75 parts of ion exchanged waters, 0.5 part of potassium rodinate, 0.1 part of uncle's lauryl mercaptan, 30 parts of (solid matter) polybutadiene latex (median sizes in the glass flask of agitator having 7 liters of internal volumes and be equipped with; 2,000 dusts, gel content; 85%) 10 parts of (solid matter) butadiene-styrene unregulated polymer latex (median sizes; 6,000 dusts, styrene content; 25%), 15 parts of vinylbenzene and 5 parts of vinyl cyanide, and under agitation heat this mixture.When internal temperature reaches 45 ℃, add 0.2 part of trisodium phosphate, 0.01 part of ferrous sulfate 7-hydrate and the solution of 0.2 part of glucose in 20 parts of ion exchanged waters.Then, add 0.07 part of cumene hydroperoxide with initiated polymerization.After carrying out polymerization one hour, added 50 parts of ion exchanged waters, 0.7 part of potassium rodi nate, 30 parts of vinylbenzene, 10 parts of vinyl cyanide, 0.05 part of uncle's lauryl mercaptan and 0.01 part of cumene hydroperoxide continuously 3 hours, the one-step polymerization one hour of going forward side by side.

Then, add 0.2 part of 2 to stop polymerization.Condense with the latex of aqueous sulfuric acid, wash with water also dry then and acquisition rubber enhancing styrene resin D1 this reaction product.The percentage of grafting of this resin D1 is 68%, and the limiting viscosity of acetone soluble material (η) is 0.45dl/g.

[0094]

(4-2) preparation embodiment 8; The AS resin

Two are had 30 liters internal volume and are equipped with the polymerization container of the chuck equipment of zonate frond to link together and use nitrogen purging.In first reaction vessel, add 75 parts of vinylbenzene, 25 parts of vinyl cyanide and 20 parts of toluene continuously.With the solution of 0.12 part of uncle's dodecyl mercaptans and 5 parts of toluene as molecular weight regulator and 0.1 part 1,1 '-solution of azo two (hexanaphthene-1-nitrile) and 5 parts of toluene is this first reaction vessel feed continuously as polymerization starter.In first container, the controlled polymerization temperature is at 110 ℃, and mean residence time is 2.0 hours, and polymerisation conversion is 57%.By extracting continuously with the pump that is provided at the first reaction vessel outside polymers soln of gained is infeeded second reaction vessel with the amount identical with the feed rate of described vinylbenzene, vinyl cyanide, toluene, molecular weight regulator and polymerization starter.In second container, polymerization temperature is in 130 ℃, and polymerisation conversion is 75%.To supply with twin screw 3-graduated discharge forcing machine so that directly evaporate unreacted monomer and solvent from the copolymer solution that second reaction vessel obtains, to obtain to have the styrene resin D2 of limiting viscosity [η] 0.48dl/g.

[0095]

(4-3) preparation embodiment 9; Rubber strengthens styrene resin

(4-3-1) The preparation of rubbery polymer (D3a)

Drying is equipped with the autoclave of agitator and chuck and uses nitrogen purging, and the solution of 20 parts of hexanaphthenes and divinyl is placed on wherein.Then, add n-Butyl Lithium, and under 50 ℃, carry out the isothermal polymerization.Reach at 100% o'clock at transformation efficiency, add 0.75 part of tetrahydrofuran (THF) and 65 parts of divinyl, and heat up from 50 ℃ and to be aggregated to 80 ℃.Reach at 100% o'clock at transformation efficiency, to wherein adding 15 parts of vinylbenzene, the step of going forward side by side is carried out polyreaction to obtain unhydrided triblock copolymer A-B1-B2.The polymkeric substance that is obtained is made up of 15% styrene block (A), 65% butadiene block (B1) and 20% butadiene block (B2), simultaneously this butadiene block (B1) have 35% 1, the 2-contents of ethylene, this butadiene block (B2) have 10% 1, the 2-contents of ethylene, this polymkeric substance has 200,000 number-average molecular weight.

In container independently, 1 part of cyclopentadienyl titanium dichloride is dispersed in the hexanaphthene, and at room temperature with 0.5 part of triethyl aluminum reaction.The homogeneous solution that is obtained is added in the above-mentioned polymers soln, and under 50 ℃ at 50kgf/cm ²Hydrogen pressure under carry out hydrogenation and become basically 100% up to hydrogenating rate, to obtain rubbery polymer D3a.

[0096]

(4-3-2) Rubber strengthens the preparation of styrene resin (D3)

The autoclave that is equipped with zonate frond and makes with nitrogen purging by stainless steel, then under nitrogen gas stream to wherein adding 28 parts (solid matter) above-mentioned polymkeric substance D3a as the homogeneous solution for preparing in advance in the toluene of solvent, 10.8 parts of vinylbenzene, 7.2 parts of vinyl cyanide, 54 parts of methyl methacrylates, 120 parts of toluene and 0.1 part of uncle's dodecyl mercaptans, and under agitation heat this mixture.When internal temperature reaches 50 ℃, to wherein adding 0.5 part of benzoyl peroxide and 0.1 part of dicumyl peroxide, and further improve temperature.Reach after 80 ℃ in temperature, controlled temperature constant at 80 ℃ to carry out polymerization.After initiated polymerization six hours, in one hour, temperature is brought up to 120 ℃, and then carried out polymerization two hours, then termination reaction.Transformation efficiency is 97%.

Be cooled to after 100 ℃ at reaction mixture, to wherein adding 0.2 part 2,2-methylene-bis-4-6-tert.-butyl phenol.Then, from this autoclave, discharge reaction mixture, distill out unreacted matters and solvent by vapor distillation then.In degassing extruder, the resulting polymers granulation is obtained polymkeric substance D3.Its percentage of grafting is 45%, and the limiting viscosity of acetone soluble material [η] is 0.45dl/g.

[0097]

(4-4) preparation embodiment 10; Rubber strengthens styrene resin

With with prepare embodiment 9 in the same method carry out polyreaction, difference is to use 19 parts of ethylene-propylene rubber (＂ EP84 ＂ (trade(brand)name), make by JSR Corporation) replace rubbery polymer D3a and use 57 parts of vinylbenzene and 24 parts of vinyl cyanide replacement styrene/acrylonitrile/methyl methacrylates, and acquisition polymkeric substance D4, it has 20% ethylene-propylene rubber content, the limiting viscosity [η] of the acetone soluble material of 55% percentage of grafting and 0.45dl/g.

[0098]

(5) component (E)

Use is by Sanko Chemical Industries, and the following polymkeric substance that Ltd. makes is as component of the present invention (E).

E1; SANKONOL AQ-50T (trade(brand)name): 50% aqueous solution of trifluoromethayl sulfonic acid lithium.

E2; SANKONOL 0862-20T (trade(brand)name): 20% solution of trifluoromethayl sulfonic acid lithium in di butoxyethoxyethyl adipate.

(6) other component;

Following material is used as other component to improve static resistance.

F1; Non-ionic antistatic agent; ELECTROSTRIPPER TS-5 (trade(brand)name; Glyceryl ester by the KaoCorporation preparation)

G1; ZnOw; PANATETPA WZ-0501 (trade(brand)name; By MatsushitaElectric Industrial Co., the Ltd. preparation).

[0099]

Example I-1 is to I-19 and I-35 to I-40, comparative example I-1 to I-10

Blending ratio shown in the 1-2 mixes component by table 1-1 and table in the Henschel mixing machine, then this mixture of melt kneading and obtain pellet in exhaust twin screw extruder (bowl temperature is set to 220 ℃).When the G1 in the middle of above-mentioned other component of use, it is supplied with the middle part of this forcing machine.The pellet that is obtained is dry fully, and then with this pellet injection molding, and acquisition is used to estimate the test specimen of antistatic property, chemical-resistant, shock-resistance, molded article surface outward appearance and thermostability.Evaluation result is shown in table 1-1 and the table 1-2.

[0100]

Example I-20 is to I-25, I-41 and I-42

Blending ratio by the anti-static resin composition shown in the table 2 in the Henschel mixing machine mixes component, then this mixture of melt kneading and obtain pellet in exhaust twin screw extruder (bowl temperature is set to 220 ℃).When the G1 in the middle of above-mentioned other component of use, it is supplied with the middle part of this forcing machine.The pellet that is obtained is dry fully, prepare three-layer tablet material (thickness by multilayer forcing machine (processing temperature is at 190-240 ℃) then with T-mould; 1.0mm), it comprises preceding and back layer (every layer thickness of being made by the anti-static resin composition of above-mentioned granulation; 0.1mm) and the core component (thickness made by the composition with blending ratio shown in the table 2; 0.8mm).

According to above-mentioned evaluation method the three-layer tablet material that is obtained is used for measuring antistatic property, chemical-resistant, shock-resistance, appearance, ion leaching and thermostability.Evaluation result is shown in the table 2.

In addition, by the above-mentioned three-layer tablet material of vacuum moulding (heater temperature; 400 ℃, warm up time; 30-45sec) the moulding disc of acquisition appearance excellence.

[0101]

Example I-26 is to I-34

Blending ratio by the anti-static resin composition shown in the table 3 in the Henschel mixing machine mixes component, then this mixture of melt kneading and obtain pellet in exhaust twin screw extruder (bowl temperature is set to 220 ℃).When the G1 in the middle of above-mentioned other component of use, it is supplied with the middle part of this forcing machine.The pellet that is obtained is dry fully, the anti-static resin composition of granulation like this is expanded (170 ℃), be the film of 50 μ m and obtain thickness.

According to above-mentioned evaluation method the film that is obtained is used for measuring antistatic property, appearance, ion leaching and thermostability.Evaluation result is shown in the table 3.

[0102]

Example I-43 is to I-46

Blending ratio by the anti-static resin composition shown in the table 3 in the Henschel mixing machine mixes component, then this mixture of melt kneading and obtain pellet in exhaust twin screw extruder (bowl temperature is set to 220 ℃).The pellet that is obtained is dry fully, prepare three-layer tablet material (thickness by multilayer forcing machine (processing temperature is at 180-200 ℃) then with T-mould; 3mm), it comprises preceding and back layer (every layer thickness of being made by the anti-static resin composition of above-mentioned granulation; 30 μ m) with by composition with blending ratio shown in the table 3 by the expand core component of about twice of blend azodicarbonamide foaming agent.

According to above-mentioned evaluation method the three-layer tablet material that is obtained is used for measuring antistatic property, chemical-resistant, appearance, ion leaching and thermostability.Evaluation result is shown in the table 3.

[0107]

Draw following from the result shown in table 1-1 and the table 1-2.

Example I-1 to I-8 be embodiment and the comparative example relevant with I-37 and comparative example I-1 to I-4 with the present invention's first anti-static resin composition.These embodiment are being excellent aspect appearance, thermostability and the anti-ion leachability of static resistance, chemical-resistant, moulded product.On the contrary, in comparative example I-1, ionic leaching amount is higher than 3 μ g/cm ²At comparative example I-2, static resistance is higher than 1 * 10 ¹¹Ω/.Comparative example I-3 is relatively poor aspect static resistance, and the amount to be used of component wherein of the present invention (A) surpasses the scope of the invention, and the amount to be used of component (B) is lower than the scope of the invention.Comparative example I-4 is relatively poor aspect chemical-resistant, molded article surface outward appearance and thermostability, and ion leaching amount aspect is higher, the amount to be used of component wherein of the present invention (A) is lower than the scope of the invention, and the amount to be used of component (B) surpasses the scope of the invention.

Example I-9 to I-19, I-35 to I-36 be embodiment and the comparative example relevant with I-38 to I-40 and comparative example I-5 to I-10 with the present invention's second anti-static resin composition.These embodiment are being excellent aspect appearance, thermostability, anti-ion leachability and the shock-resistance of static resistance, chemical-resistant, moulded product.On the contrary, in comparative example I-5, ionic leaching amount is higher than 3 μ g/cm ²At comparative example I-6, static resistance is higher than 1 * 10 ¹¹Ω/.Comparative example I-7 is relatively poor aspect static resistance, chemical-resistant, shock-resistance and molded article surface outward appearance, and the amount to be used of component wherein of the present invention (A) is lower than the scope of the invention.Comparative example I-8 is relatively poor aspect shock-resistance, and the amount to be used of component wherein of the present invention (C) is lower than the scope of the invention.Comparative example I-9 is relatively poor aspect static resistance, and the amount to be used of component wherein of the present invention (B) is lower than the scope of the invention.Comparative example I-10 is relatively poor aspect static resistance and chemical-resistant, and the amount to be used of component wherein of the present invention (D) surpasses the scope of the invention.

Draw to draw a conclusion from the result shown in the table 2.

Example I-20 to I-25, I-41 be excellent with I-42 (they are and the relevant embodiment of sheet material that is made by the present invention's second anti-static resin composition) aspect static resistance, chemical-resistant, sheet surface outward appearance, shock-resistance and the anti-ion leachability, and aspect vacuum formability, be excellent further.Draw following from the result shown in the table 3.

Example I-26 to I-34 (they are and the relevant embodiment of film that is made by the present invention's first anti-static resin composition) be excellent aspect static resistance, film surface outward appearance and the anti-ion leachability.In addition, example I-43 to I-46 (they are embodiments relevant with moulded product, and described moulded product has the film of being made by the present invention's second anti-static resin composition that is laminated on the foam substrate) be excellent aspect static resistance, chemical-resistant, appearance, thermostability and the anti-ion leachability.

[0108]

Example II-1 is to II-18 and II-26 to II-31, comparative example II-1 to II-10

Blending ratio shown in the 4-2 mixes component by table 4-1 and table in the Henschel mixing machine, then this mixture of melt kneading and obtain pellet in exhaust twin screw extruder (bowl temperature is set to 220 ℃).When the G1 in the middle of above-mentioned other component of use, it is supplied with the middle part of this forcing machine.The pellet that is obtained is dry fully, and then with this pellet injection molding (bowl temperature is set to 220 ℃), and acquisition is used to estimate the test specimen of antistatic property, chemical-resistant, shock-resistance, molded article surface outward appearance and thermostability.Evaluation result is shown in table 4-1 and the table 4-2.

[0109]

Example II-19 is to II-22, II-32 and II-33

Blending ratio by the anti-static resin composition shown in the table 5 in the Henschel mixing machine mixes component, then this mixture of melt kneading and obtain pellet in exhaust twin screw extruder (bowl temperature is set to 220 ℃).When the G1 in the middle of above-mentioned other component of use, it is supplied with the middle part of this forcing machine.The pellet that is obtained is dry fully, prepare three-layer tablet material (thickness by multilayer forcing machine (processing temperature is at 190-240 ℃) then with T-mould; 1.0mm), it comprises preceding and back layer (every layer thickness of being made by the anti-static resin composition of above-mentioned granulation; 0.1mm) and the core component (thickness made by the composition with blending ratio shown in the table 5; 0.8mm).

According to above-mentioned evaluation method the three-layer tablet material that is obtained is used for measuring antistatic property, chemical-resistant, shock-resistance, appearance, ion leaching and thermostability.Evaluation result is shown in the table 5.

In addition, by the above-mentioned three-layer tablet material of vacuum moulding (heater temperature; 400 ℃, warm up time; 30-45sec) the moulding disc of acquisition appearance excellence.

[0110]

Example II-23 is to II-25

Blending ratio by the anti-static resin composition shown in the table 6 in the Henschel mixing machine mixes component, then this mixture of melt kneading and obtain pellet in exhaust twin screw extruder (bowl temperature is set to 220 ℃).The pellet that is obtained is dry fully, the anti-static resin composition of granulation like this is expanded (170 ℃), be the film of 50 μ m and obtain thickness.According to above-mentioned evaluation method the film that is obtained is used for measuring antistatic property, appearance, ion leaching and thermostability.Evaluation result is shown in the table 6.

[0111]

Example II-34 is to II-37

Blending ratio by the anti-static resin composition shown in the table 6 in the Henschel mixing machine mixes component, then this mixture of melt kneading and obtain pellet in exhaust twin screw extruder (bowl temperature is set to 220 ℃).The pellet that is obtained is dry fully, prepare three-layer tablet material (thickness by multilayer forcing machine (processing temperature is at 180-200 ℃) then with T-mould; 3.0mm), it comprises preceding and back layer (every layer thickness of being made by the anti-static resin composition of above-mentioned granulation; 30 μ m) with by composition with blending ratio shown in the table 6 by the expand core component of about twice of blend azodicarbonamide foaming agent.

According to above-mentioned evaluation method the three-layer tablet material that is obtained is used for measuring antistatic property, chemical-resistant, appearance, ion leaching and thermostability.Evaluation result is shown in the table 6.

[0112]

[0116]

Draw following from the result shown in table 4-1 and the table 4-2.

Example II-1 to II-7 be embodiment and the comparative example relevant with II-26 and comparative example II-1 to II-4 with the present invention's first anti-static resin composition.These embodiment are being excellent aspect the appearance of static resistance, chemical-resistant, moulded product and the anti-ion leachability.

On the contrary, in comparative example II-1, static resistance is higher than 1 * 10 ¹¹Ω/.Comparative example II-2 is relatively poor aspect static resistance, and the amount to be used of component wherein of the present invention (A) surpasses the scope of the invention, and the amount to be used of component (B) is lower than the scope of the invention.Comparative example II-3 is relatively poor aspect the appearance of chemical-resistant, moulded product and thermostability, and the amount to be used of component wherein of the present invention (A) is lower than the scope of the invention, and the amount to be used of component (B) surpasses the scope of the invention.In comparative example II-4, ionic leaching amount surpasses the scope of the invention.

Example II-8 to II-18 be embodiment and the comparative example relevant with II-27 to II-31 and comparative example II-5 to II-10 with the present invention's second anti-static resin composition.These embodiment are being excellent aspect appearance, thermostability, anti-ion leachability and the shock-resistance of static resistance, chemical-resistant, moulded product.

On the contrary, in comparative example II-5, static resistance is higher than 1 * 10 ¹¹Ω/.Comparative example II-6 is relatively poor aspect the appearance of moulded product and shock-resistance, and the amount to be used of component wherein of the present invention (E) surpasses the scope of the invention.In comparative example II-7, ionic leaching amount surpasses the scope of the invention.Comparative example II-8 is relatively poor aspect shock-resistance, and the amount to be used of component wherein of the present invention (C) is lower than the scope of the invention.Comparative example II-9 is relatively poor aspect static resistance and chemical-resistant, and the amount to be used of component wherein of the present invention (D) surpasses the scope of the invention.Comparative example II-10 is relatively poor aspect static resistance, and the amount to be used of component wherein of the present invention (B) is lower than the scope of the invention.

Draw following from the result shown in the table 5.

Example II-19 to II-22, II-32 be excellent with II-33 (they are and the relevant embodiment of sheet material that is made by the present invention's second anti-static resin composition) aspect static resistance, chemical-resistant, sheet surface outward appearance, shock-resistance and the anti-ion leachability, and aspect vacuum formability, be excellent further.

Draw following from the result shown in the table 6.

Example II-23 to II-25 (they are and the relevant embodiment of film that is made by the present invention's first anti-static resin composition) be excellent aspect static resistance, film surface outward appearance and the anti-ion leachability.In addition, example II-34 to II-37 (they are embodiments relevant with moulded product, and described moulded product comprises the film of being made by the present invention's second anti-static resin composition that is laminated on the foam substrate) be excellent aspect static resistance, chemical-resistant, appearance, thermostability and the anti-ion leachability.

Industrial applicability

[0117]

Anti-static resin composition of the present invention with compared in the past antistatic behaviour, chemical-resistant, Molded article surface outward appearance and heat endurance are more excellent, and ion leaching amount is lower, so it can be fitted Close in wherein requiring high performance field for example vehicular field, electric/electronic field, office Various parts in chamber automation (OA) and household appliance technical field and the health product field.

Claims (20)

1. anti-static resin composition, it comprises following component of 40-98 quality % (A) and the following component of 2-60 quality % (B), condition is that said components (A) and total amount (B) are 100 quality %, and wherein when said composition was molded as goods, described composition had 1 * 10 ¹¹Ω/ or lower surface resistivity (under the condition of 23 ℃ and 50%R.H., measuring) and 3 μ g/cm ²Or lower sodium and potassium ion leaching amount (under the condition of 80 ℃ and extraction in 60 minutes, measuring).

Component (A): olefin resin; With

Component (B): the segmented copolymer that comprises olefin polymer block and hydrophilic polymer block.

2. according to the anti-static resin composition of claim 1, wherein said components (B) is that total content that 1/99-90/10 comprises sodium and potassium is that the total content of the segmented copolymer (B-1) of 500-8000ppm and sodium and potassium is the segmented copolymer (B-2) of 0-100ppm and with this segmented copolymer of amount blend (B-1) with respect to said components (A) and total amount 1-15 quality % (B) by segmented copolymer (B-1) with respect to the mass ratio of segmented copolymer (B-2).

3. according to the anti-static resin composition of claim 2, the sodium and/or the potassium that wherein are included in the above-mentioned segmented copolymer (B-1) are sulfonate form.

4. according to the anti-static resin composition of claim 2 or 3, it also comprises 0.01-5 mass parts lithium salts (E), with respect to 100 mass parts said components (A) and total amounts (B).

5. according to the anti-static resin composition of claim 4, wherein above-mentioned lithium salts (E) is to be selected from least a in lithium perchlorate, trifluoromethayl sulfonic acid lithium, two (trifluoromethane sulphonyl) imines lithiums and three (trifluoromethane sulfonyl group) methane lithium.

6. according to the anti-static resin composition of claim 1, it also comprises 0.01-5 mass parts lithium salts (E), with respect to 100 mass parts said components (A) and total amounts (B).

7. according to the anti-static resin composition of claim 6, wherein component (B) has the sodium of 0-1000ppm and the total content of potassium.

8. according to the anti-static resin composition of claim 6 or 7, wherein above-mentioned lithium salts (E) is selected from least a in lithium perchlorate, trifluoromethayl sulfonic acid lithium, two (trifluoromethane sulphonyl) imines lithiums and three (trifluoromethane sulfonyl group) methane lithium.

9. according to each anti-static resin composition among the claim 6-8, the sodium and/or the potassium that wherein are included in the said components (B) are sulfonate form.

10. anti-static resin composition, it comprises the following component of 7-91 quality % (A), the following component of 2-60 quality % (B), the following component of 2-50 quality % (C) and the following component of 5-50 quality % (D), condition is that said components (A), (B), (C) and total amount (D) are 100 quality %, and wherein said composition has 1 * 10 ¹¹Ω/ or lower surface resistivity (under the condition of 23 ℃ and 50%R.H., measuring) and 3 μ g/cm ²Or lower sodium and potassium ion leaching amount (under the condition of 80 ℃ and extraction in 60 minutes, measuring).

Component (A): olefin resin;

Component (B): the segmented copolymer that comprises olefin polymer block and hydrophilic polymer block;

Component (C): at least a elastomerics, it is selected from the segmented copolymer of the polymer blocks that comprises mainly the polymer blocks is made up of aromatic vinyl compound and mainly be made up of conjugated diene compound and its hydrogenated products; With

Component (D): styrene resin, its rubber that comprises by make the polymerization of vinyl monomer acquisition that comprises aromatic vinyl compound in the presence of rubbery polymer strengthens styrene polymer (D-1), and/or (being total to) polymkeric substance (D-2) of described vinyl monomer.

11. according to the anti-static resin composition of claim 10, wherein said components (B) is to be that total content that 1/99-90/10 comprises sodium and potassium is that the total content of the segmented copolymer (B-1) of 500-8000ppm and sodium and potassium is the segmented copolymer (B-2) of 0-100ppm and with this segmented copolymer of amount blend (B-1) with respect to said components (A), (B), (C) and total amount 1-15 quality % (D) by segmented copolymer (B-1) with respect to the mass ratio of segmented copolymer (B-2).

12. according to the anti-static resin composition of claim 11, the sodium and/or the potassium that wherein are included in the above-mentioned segmented copolymer (B-1) are sulfonate form.

13. according to the anti-static resin composition of claim 11 or 12, it also comprises 0.01-5 mass parts lithium salts (E), with respect to 100 mass parts said components (A), (B), (C) and total amount (D).

14. according to the anti-static resin composition of claim 13, wherein above-mentioned lithium salts (E) is to be selected from least a in lithium perchlorate, trifluoromethayl sulfonic acid lithium, two (trifluoromethane sulphonyl) imines lithiums and three (trifluoromethane sulfonyl group) methane lithium.

15. according to the anti-static resin composition of claim 10, it also comprises 0.01-5 mass parts lithium salts (E), with respect to 100 mass parts said components (A), (B), (C) and total amount (D).

16. according to the anti-static resin composition of claim 15, wherein component (B) has the sodium of 0-1000ppm and the total content of potassium.

17. according to the anti-static resin composition of claim 15 or 16, wherein above-mentioned lithium salts (E) is to be selected from least a in lithium perchlorate, trifluoromethayl sulfonic acid lithium, two (trifluoromethane sulphonyl) imines lithiums and three (trifluoromethane sulfonyl group) methane lithium.

18. according to each anti-static resin composition among the claim 15-17, the sodium and/or the potassium that wherein are included in the said components (B) are sulfonate form.

19. by the moulded product of making according to each anti-static resin composition among the claim 1-18.

20. by sheet material or the film made according to each anti-static resin composition among the claim 1-18.