CN101659774A

CN101659774A - Styrene copolymer composite

Info

Publication number: CN101659774A
Application number: CN200910173559A
Authority: CN
Inventors: 星进; 久保伸明
Original assignee: Asahi Kasei Kogyo KK
Current assignee: Asahi Kasei Corp
Priority date: 2000-06-30
Filing date: 2000-06-30
Publication date: 2010-03-03

Abstract

The invention discloses styrene copolymer composite. The styrene copolymer composite comprises styrene/n-butyl acrylate copolymer (I) containing styrene monomeric unit and n-butyl acrylate monomeric unit in a ratio of 80/20-89/11 and block copolymer (II) containing at least two polymer blocks (A) which are mainly composed of vinyl aromatic monomer and at least one kind of vinyl arene/conjugated diene polymer block (B), wherein the ratio of the vinyl aromatic monomer to the conjugated diene monomer is 65/35-90/10. In the copolymer (II), the weight ratio of heaviest block of the at least two polymer blocks (A) to the lightest is 1.2-4.5 or 1.0-1.2, not including 1.2.

Description

Styrene copolymer composite

The application be that June 30, application number in 2000 are 00813477.4 the applying date, invention and created name divides an application for the application of " styrene copolymer composite ".

Technical field

The present invention relates to a kind ofly comprise styrene/acrylic n-butyl multipolymer (I) and comprise vinyl aromatic monomer unit and the styrene copolymer composite of the segmented copolymer of conjugated diene monomeric unit (II).More particularly, the present invention relates to a kind of styrene copolymer composite, comprise: comprise the styrene monomer unit of specific ratios and the styrene/acrylic n-butyl multipolymer (I) of n-butylacrylate monomeric unit, with have the polymer blocks (A) that comprises at least two kinds of difference and mainly form by vinyl aromatic monomer unit, segmented copolymer (II) with the block configuration of at least a vinyl-arene/conjugated diene copolymer block (B), described segmented copolymer (II) comprises the vinyl aromatic monomer unit and the conjugated diene monomeric unit of specific ratios, wherein the vinyl aromatic monomer unit of segmented copolymer (II) partly has the vinyl aromatic monomer unit in the short chain section that being included in of specific ratios be made up of 1-3 vinyl aromatic monomer unit, wherein polymer blocks (A) comprises showing the peak-peak molecular weight and have the peak-peak polydispersity polymer block of at least one peak molecular weight in the gel permeation chromatography of polymer blocks (A) in the specific molecular weight range of specified quantitative, wherein polymer blocks (A) has maximum weight polymer blocks and minimum weight polymer blocks, wherein the weight ratio of maximum weight polymer blocks and minimum weight polymer blocks is bigger, and wherein the weight ratio of styrene/acrylic n-butyl multipolymer (I) and segmented copolymer (II) in specified range.The invention still further relates to a kind of styrene copolymer composite, comprise: comprise the styrene monomer unit of specific ratios and the styrene/acrylic n-butyl multipolymer (I) of n-butylacrylate monomeric unit, with have the polymer blocks (A) that comprises at least two kinds of difference and mainly form by vinyl aromatic monomer unit, segmented copolymer (II) with the block configuration of at least a vinyl-arene/conjugated diene copolymer block (B), described segmented copolymer (II) comprises vinyl aromatic monomer unit and conjugated diene monomeric unit, wherein the vinyl aromatic monomer unit of segmented copolymer (II) partly has the vinyl aromatic monomer unit in the short chain section that being included in of specific ratios be made up of 1-3 vinyl aromatic monomer unit, wherein polymer blocks (A) comprises the polymer blocks with peak molecular weight of specified quantitative, described block shows at least one peak molecular weight in the specific molecular weight range in the gel permeation chromatography of polymer blocks (A), wherein polymer blocks (A) has maximum weight polymer blocks and minimum weight polymer blocks, wherein the weight ratio of maximum weight polymer blocks and minimum weight polymer blocks is less, and wherein the weight ratio of styrene/acrylic n-butyl multipolymer (I) and segmented copolymer (II) in specified range.(below, the segmented copolymer (II) that the segmented copolymer (II) that comprises the polymer blocks (A) of at least two kinds of maximum weight polymer blocks with big weight ratio and minimum weight polymer blocks often is called " asymmetric segmented copolymer (II) " and comprises the polymer blocks (A) of at least two kinds of maximum weight polymer blocks with lower weight ratio and minimum weight polymer blocks often is called " symmetrical segmented copolymer (II) ").

The moulded products that is obtained by styrene copolymer composite of the present invention not only has high tensile modulus, high elongation at tear, the excellent transparency, low nature shrinkage coefficient (promptly, low-shrinkage at ambient temperature) and in hot water to the high patience of fusion bonding (for example, low melt cohesiveness in the hot water of 85 ℃ of temperature), and the flake that does not have obviously to occur (below, " flake " often is called " FE " simply).In addition, if styrene copolymer composite of the present invention comprises above-mentioned asymmetric segmented copolymer (II), moulded products therefrom also has excellent surface impacts intensity.On the other hand, if styrene copolymer composite of the present invention comprises above-mentioned symmetrical segmented copolymer (II), moulded products therefrom also advantageously has less anisotropy.In addition, by introducing specific additive in styrene copolymer composite of the present invention, can effectively being suppressed in the moulded products therefrom (as sheet material or film) FE appears.

In addition, the hot shrinkable films that is obtained by styrene copolymer composite of the present invention does not only have the obviously FE of appearance, but also has excellent hot contractility under low Heating temperature.

Background technology

The content higher segmented copolymer that comprises vinyl aromatic monomer unit and conjugated diene monomeric unit in therein ethylene base aromatic monomer unit has various excellent specific properties, as the transparency and impact-resistance, so these segmented copolymers have been used to produce injecting products, extruded product (as sheet material and film) and analogue.In addition, the polymer composition that comprises above-mentioned segmented copolymer and vinyl-arene/aliphatic olefinically unsaturated carboxylic acid derivatives multipolymer has the excellent transparency, mechanical property and shrinkability, so said composition has been used to produce sheet material, film and analogue.

For above-mentioned polymer composition and sheet material therefrom and film, many schemes are proposed in patent document usually.For example, not only has a high tensile as a kind of, modulus and shock strength, but also has excellent optical, the composition of elongation performance and resistance to cracking etc., do not examine Japanese Patent Application Publication specification sheets № 59-221348 and disclose a kind of polymer composition, comprise, vinyl-arene/aliphatic olefinically unsaturated carboxylic acid derivatives multipolymer, with the multipolymer that comprises at least a vinyl aromatic polymer block and at least a polymer blocks of mainly being made up of conjugated diolefine, aliphatic olefinically unsaturated carboxylic acid derivatives content and Vicat softening point that therein ethylene base aromatic hydrocarbons/aliphatic olefinically unsaturated carboxylic acid derivatives multipolymer has 5-80% weight are 90 ℃ or lower.As a kind of hot contractility under low Heating temperature with excellence, optical characteristics, resistance to cracking, the hot shrinkable films of dimensional stability etc., examine Japanese Patent Application Publication specification sheets № 61-25819 and disclose the film that the film by a kind of polymer composition that stretches obtains, this polymer composition comprises vinyl-arene/aliphatic olefinically unsaturated carboxylic acid derivatives multipolymer, with the multipolymer that comprises at least a vinyl aromatic polymer block and a kind of polymer blocks of mainly being made up of conjugated diolefine, vinyl aromatic content and Vicat softening point that therein ethylene base aromatic hydrocarbons/aliphatic olefinically unsaturated carboxylic acid derivatives multipolymer has 20-95% weight are 90 ℃ or lower.In addition, have the transparent of rotten property of excellent anti-time and impact-resistance as a kind of, hot shrinkable films, do not examine the rigidity that Japanese Patent Application Publication specification sheets № 5-104630 discloses a kind of polymer composition, hot shrinkable films, this polymer composition comprises vinyl-arene/aliphatic olefinically unsaturated carboxylic acid derivatives multipolymer, with the multipolymer that comprises at least a vinyl aromatic polymer block and at least a polymer blocks of mainly being made up of conjugated diolefine, the Vicat softening point of therein ethylene base aromatic hydrocarbons/aliphatic olefinically unsaturated carboxylic acid derivatives multipolymer is 105 ℃ or lower.This hot shrinkable films has the hot contractility of measuring in specified range on the film specific direction.In addition, as a kind of film that has the excellent transparency, deflection and surperficial impact-resistance at low temperatures, do not examine Japanese Patent Application Publication specification sheets № 6-220278 and disclose a kind of polymer composition, wherein comprise a kind of segmented copolymer and a kind of vinyl-arene/(methyl) acrylate copolymer resin that comprises vinyl-arene and conjugated diolefine, wherein said segmented copolymer has specific block configuration and particular molecular weight distribution.In addition, have the excellent transparency and a resin combination of impact-resistance as a kind of, do not examine Japanese Patent Application Publication specification sheets № 7-216187 and disclose a kind of high-intensity transparent resin composition that has, it comprises a kind of segmented copolymer and a kind of vinyl-arene/(methyl) acrylate copolymer, and wherein said segmented copolymer comprises two kinds of vinyl aromatic polymer blocks and two kinds of vinyl-arene/conjugated diene copolymer blocks.

But the problem of the every kind of conventional polymer composition of describing in the above-mentioned patent document that comprises segmented copolymer (comprising vinyl aromatic monomer unit and conjugated diene monomeric unit) and vinyl-arene/aliphatic olefinically unsaturated carboxylic acid derivatives multipolymer respectively is, if this conventional composition is used for producing than fine sheet or film, can not only be had high tensile modulus, high elongation at tear, high surface impacts intensity, the excellent transparency, low nature shrinkage coefficient and the high refractory in hot water and be melted cohesiveness, and do not had obviously sheet material or the film of the FE of appearance.In addition, how above-mentioned patent document is to addressing this problem without any explanation.

Summary of the invention

In this case, the inventor carries out prior art is followed in intensive research with solution the problems referred to above.The result shockingly finds, a kind of not only have a high tensile modulus, high elongation at tear, high surface impacts intensity, the excellent transparency, low nature shrinkage coefficient and the high refractory in hot water melt cohesiveness, and there is not the moulded products (as sheet material or film) of the obvious FE that occurs to make by using a kind of styrene copolymer composite, said composition comprises: comprise the styrene monomer unit of specific ratios and the styrene/acrylic n-butyl multipolymer (I) of n-butylacrylate monomeric unit, segmented copolymer (II) with block configuration with the polymer blocks (A) that comprises at least two kinds of difference and mainly form and at least a vinyl-arene/conjugated diene copolymer block (B) by vinyl aromatic monomer unit, described segmented copolymer (II) comprises the vinyl aromatic monomer unit and the conjugated diene monomeric unit of specific ratios, wherein the vinyl aromatic monomer unit of segmented copolymer (II) partly has the vinyl aromatic monomer unit in the short chain section that being included in of specific ratios be made up of 1-3 vinyl aromatic monomer unit, wherein polymer blocks (A) comprises showing the peak-peak molecular weight and have the peak-peak polydispersity polymer block of at least one peak molecular weight in the gel permeation chromatography of polymer blocks (A) in the specific molecular weight range of specified quantitative, wherein polymer blocks (A) has maximum weight polymer blocks and minimum weight polymer blocks, the weight ratio of maximum weight polymer blocks and minimum weight polymer blocks big (1.2-4.5) wherein, and wherein the weight ratio of styrene/acrylic n-butyl multipolymer (I) and segmented copolymer (II) in specified range.In addition, the inventor also finds, a kind of not only have a high tensile modulus, high elongation at tear, high surface impacts intensity, the excellent transparency, low nature shrinkage coefficient and the high refractory in hot water melt cohesiveness, and there is not the moulded products (as sheet material or film) of the obvious FE that occurs to make by using a kind of styrene copolymer composite, said composition comprises: comprise the styrene monomer unit of specific ratios and the styrene/acrylic n-butyl multipolymer (I) of n-butylacrylate monomeric unit, segmented copolymer (II) with block configuration with the polymer blocks (A) that comprises at least two kinds of difference and mainly form and at least a vinyl-arene/conjugated diene copolymer block (B) by vinyl aromatic monomer unit, described segmented copolymer (II) comprises the vinyl aromatic monomer unit and the conjugated diene monomeric unit of specific ratios, wherein the vinyl aromatic monomer unit of segmented copolymer (II) partly has the vinyl aromatic monomer unit in the short chain section that being included in of specific ratios be made up of 1-3 vinyl aromatic monomer unit, wherein polymer blocks (A) comprises the polymer blocks with peak molecular weight of specified quantitative, described block shows at least one peak molecular weight in the specific molecular weight range in the gel permeation chromatography of polymer blocks (A), wherein polymer blocks (A) has maximum weight polymer blocks and minimum weight polymer blocks, the weight ratio of maximum weight polymer blocks and minimum weight polymer blocks less (1.0 to being lower than 1.2) wherein, and wherein the weight ratio of styrene/acrylic n-butyl multipolymer (I) and segmented copolymer (II) in specified range.Based on these discoveries, the present invention is accomplished.

Therefore, a main purpose of the present invention provides a kind of styrene copolymer composite of producing excellent moulded products (as sheet material or film) that is advantageously used in, the advantage of this moulded products is not only have high tensile modulus, high elongation at tear, high surface impacts intensity, the excellent transparency, low nature shrinkage coefficient and the high refractory in hot water melt cohesiveness, and not have the obviously FE of appearance.

Another object of the present invention provides a kind of being advantageously used in and produces the styrene copolymer composite have large anisotropy slightly but to have the excellent moulded products of high surperficial resistance to impact shock and above-mentioned advantage.

A further object of the present invention provides a kind of styrene copolymer composite of producing the excellent moulded products with less anisotropy and above-mentioned advantage that is advantageously used in.

According to the following detailed description and claims and in conjunction with the accompanying drawings, obviously draw aforementioned and other purpose, characteristics and advantage of the present invention.

Description of drawings

Fig. 1 has provided and has been used for explaining a figure being used for the preferred melt viscosity scope that styrene/acrylic n-butyl multipolymer of the present invention (I) measures under 180-240 ℃ of temperature.In Fig. 1, the lower limit of the preferred melt viscosity scope of curve representation of drawing by solid line, wherein this lower limit is determined by following formula:

The lower limit of melt viscosity=1.46 * 10 ⁵-1119.2 * T+2.256 * T ²

Wherein T represent to be used for this melt viscosity the measurement temperature (℃), and

The upper limit of the preferred melt viscosity scope of curve representation of drawing by dotted line, wherein this upper limit is determined by following formula:

The upper limit of melt viscosity=2.91 * 10 ⁵-2350 * T+5 * T ²

Wherein T represent to be used for this melt viscosity the measurement temperature (℃).

Detailed description of the present invention

In one aspect of the invention, provide a kind of styrene copolymer composite, comprised:

(I) styrene/acrylic n-butyl copolymer comprises the styrene monomer of 80-89% weight The n-butylacrylate monomeric unit of unit and 20-11% weight; With

(II) have and comprise polymer blocks that (A) at least two kinds of difference mainly are made up of vinyl aromatic monomer unit and (B) block copolymer of the block configuration of at least a vinyl-arene/conjugated diene copolymer block,

Described block copolymer (II) comprises vinyl aromatic monomer unit and the 35-10% weight conjugated diene monomeric unit of 65-90% weight,

Wherein the vinyl aromatic monomer unit of block copolymer (II) partly has the short chain section ratio of 1-25% weight, wherein short chain section ratio is defined as the percetage by weight that is included in the vinyl aromatic monomer unit at least a short chain section that is made up of 1-3 vinyl aromatic monomer unit, based on the gross weight that is included in the vinyl aromatic monomer unit in the block copolymer (II)

Wherein said at least two kinds of polymer blocks (A) comprise a kind of peak-peak polydispersity polymer block that has at least one peak molecular weight in peak-peak molecular weight and the scope at 30000-150000 that shows in the gel permeation chromatography of described at least two kinds of polymer blocks (A), and the content of described peak-peak polydispersity polymer block in described at least two kinds of polymer blocks (A) is 20-50% weight

Wherein said at least two kinds of polymer blocks (A) have maximum weight polymer blocks and minimum weight polymer blocks, and wherein the weight ratio of maximum weight polymer blocks and minimum weight polymer blocks is 1.2-4.5, and

Wherein styrene/acrylic n-butyl multipolymer (I) is 10/90-90/10 with the weight ratio of segmented copolymer (II).

In another aspect of this invention, provide a kind of styrene copolymer composite, comprised:

(I) styrene/acrylic n-butyl multipolymer comprises the styrene monomer unit of 80-89% weight and the n-butylacrylate monomeric unit of 20-11% weight; With

(II) have and comprise the polymer blocks that (A) at least two kinds of difference mainly are made up of vinyl aromatic monomer unit and (B) segmented copolymer of the block configuration of at least a vinyl-arene/conjugated diene copolymer block,

Described segmented copolymer (II) comprises the vinyl aromatic monomer unit of 75-85% weight and the conjugated diene monomeric unit of 25-15% weight,

Wherein the vinyl aromatic monomer unit of segmented copolymer (II) partly has the short chain section ratio of 10-20% weight, wherein short chain section ratio is defined as the weight percentage that is included in the vinyl aromatic monomer unit at least a short chain section of being made up of 1-3 vinyl aromatic monomer unit, based on the gross weight that is included in the vinyl aromatic monomer unit in the segmented copolymer (II)

Wherein said at least two kinds of polymer blocks (A) comprise a kind of polymer blocks with peak molecular weight that shows at least one peak molecular weight in the 20000-70000 scope at least in the gel permeation chromatography of described two kinds of polymer blocks (A), and the described content of polymer blocks in described at least two kinds of polymer blocks (A) with peak molecular weight is 25-35% weight

Wherein said at least two kinds of polymer blocks (A) have maximum weight polymer blocks and minimum weight polymer blocks, and wherein the weight ratio of maximum weight polymer blocks and minimum weight polymer blocks is 1.0 to being lower than 1.2, and

Wherein styrene/acrylic n-butyl multipolymer (I) is 20/80-60/40 with the weight ratio of segmented copolymer (II).

For the ease of understanding the present invention, below enumerate essential characteristic of the present invention and various preferred embodiment.

1. styrene copolymer composite comprises:

Described segmented copolymer (II) comprises the vinyl aromatic monomer unit and the 35-10% weight conjugated diene monomeric unit of 65-90% weight,

Wherein the vinyl aromatic monomer unit of segmented copolymer (II) partly has the short chain section ratio of 1-25% weight, wherein short chain section ratio is defined as the weight percentage that is included in the vinyl aromatic monomer unit at least a short chain section of being made up of 1-3 vinyl aromatic monomer unit, based on the gross weight that is included in the vinyl aromatic monomer unit in the segmented copolymer (II)

2. according to above 1 styrene copolymer composite, wherein styrene/acrylic n-butyl multipolymer (I) comprises the styrene monomer unit of 83-89% weight and the n-butylacrylate monomeric unit of 17-11% weight.

3. according to above 1 or 2 styrene copolymer composite, it can access mist degree is 1.2% or lower moulded products.

4. according to any one styrene copolymer composite among above the 1-3, wherein the melt viscosity P (T) that measures under 180-240 ℃ temperature of styrene/acrylic n-butyl multipolymer (I) satisfies following formula:

1.46×10 ⁵-1119.2×T+2.256×T ²≤P(T)≤2.91×10 ⁵-2350×T+5×T ²

Wherein T represent to be used for this melt viscosity the measurement temperature (℃) and P (T) represent this multipolymer (I) temperature T (℃) melt viscosity (pool) measured down.

5. according to any one styrene copolymer composite among above the 1-4, wherein styrene/acrylic n-butyl multipolymer (I) is 1.5 * 10 30 ℃ of storage moduluss of measuring down ⁹-2.5 * 10 ⁹Pa, and wherein the temperature of this multipolymer (I) when relatively the storage modulus under 30 ℃ shows 50% storage modulus is 75-100 ℃.

6. according to any one styrene copolymer composite among above the 1-5, it also comprises 0.05-3 parts by weight of acrylic acid 2-(1-(the 2-hydroxyl-3 as stablizer, the 5-di-tert-pentyl-phenyl) ethyl)-4,6-di-tert-pentyl-phenyl ester, the styrene/acrylic n-butyl multipolymer (I) of relative 100 weight parts and the summation of segmented copolymer (II).

7. styrene copolymer composite comprises:

8. according to above 7 styrene copolymer composite, wherein styrene/acrylic n-butyl multipolymer (I) comprises the styrene monomer unit of 83-89% weight and the n-butylacrylate monomeric unit of 17-11% weight.

9. according to above 7 or 8 styrene copolymer composite, it can access mist degree is 1.2% or lower moulded products.

10. according to any one styrene copolymer composite among above the 7-9, wherein the melt viscosity P (T) that measures under 180-240 ℃ temperature of styrene/acrylic n-butyl multipolymer (I) satisfies following formula:

1.46×10 ⁵-1119.2×T+2.256×T ²≤P(T)≤2.91×10 ⁵-2350×T+5×T ²

11. according to any one styrene copolymer composite among above the 7-10, wherein styrene/acrylic n-butyl multipolymer (I) is 1.5 * 10 30 ℃ of storage moduluss of measuring down ⁹-2.5 * 10 ⁹Pa, and wherein the temperature of this multipolymer (I) when relatively the storage modulus under 30 ℃ shows 50% storage modulus is 75-100 ℃.

12. according to any one styrene copolymer composite among above the 7-11, it also comprises 0.05-3 parts by weight of acrylic acid 2-(1-(the 2-hydroxyl-3 as stablizer, the 5-di-tert-pentyl-phenyl) ethyl)-4,6-di-tert-pentyl-phenyl ester, the styrene/acrylic n-butyl multipolymer (I) of relative 100 weight parts and the summation of segmented copolymer (II).

Below describe the present invention in detail.

In the present invention, the monomeric unit of polymkeric substance is named according to nomenclature, wherein monomeric unit derived from the title of original monomer use with additional term " unit " on it.For example, term " vinyl aromatic monomer unit " is meant a kind of monomeric unit that forms in the polymkeric substance that the polyreaction by vinyl aromatic monomer obtains.Vinyl aromatic monomer unit has a kind of molecular structure, wherein forms keyed jointing with adjacent vinyl aromatic monomer unit respectively derived from two carbon atoms of the substituted ethylene of substituted ethylene base.Similarly, term " conjugated diene monomeric unit " is meant a kind of monomeric unit that forms in the polymkeric substance that the polyreaction by conjugate diene monomer obtains.Conjugated diene monomeric unit has a kind of molecular structure, wherein forms keyed jointing with adjacent conjugated diene monomeric unit respectively derived from two carbon atoms of the alkene of conjugate diene monomer.

In the present invention, as mentioned above, a kind of styrene copolymer composite is provided, comprise: (I) comprise the styrene monomer unit of specific ratios and the styrene/acrylic n-butyl multipolymer of n-butylacrylate monomeric unit, (II) have and comprise the polymer blocks that (A) at least two kinds of difference mainly are made up of vinyl aromatic monomer unit and (B) segmented copolymer of the block configuration of at least a vinyl-arene/conjugated diene copolymer block, described segmented copolymer (II) comprises the vinyl aromatic monomer unit and the conjugated diene monomeric unit of specific ratios.In a first aspect of the present invention, provide a kind of styrene copolymer composite that comprises above-mentioned " asymmetric segmented copolymer (II) ".In a second aspect of the present invention, provide a kind of styrene copolymer composite that comprises above-mentioned " symmetrical segmented copolymer (II) ".

At first explain the styrene/acrylic n-butyl multipolymer (I) of the every kind of composition that is used for first and second aspects.

Be used for styrene/acrylic n-butyl multipolymer of the present invention (I) and comprise the styrene monomer unit of 80-89% weight and the n-butylacrylate monomeric unit of 20-11% weight.The styrene monomer unit content of styrene/acrylic n-butyl multipolymer (I) is preferably 83-89% weight.If the styrene monomer unit content of styrene/acrylic n-butyl multipolymer (I) is lower than 80% weight, often produce shortcoming, wherein fusion bonding (as, the fusion bonding between sheet material) takes place in sheet material of being made by styrene copolymer composite or film at a lower temperature.If the styrene monomer unit content of styrene/acrylic n-butyl multipolymer (I) surpasses 89% weight, the transparency of the moulded products of being made by styrene copolymer composite is step-down unfriendly.

The melt viscosity P (T) that styrene/acrylic n-butyl multipolymer (I) is measured under 180-240 ℃ temperature preferably satisfies following formula:

1.46×10 ⁵-1119.2×T+2.256×T ²≤P(T)≤2.91×10 ⁵-2350×T+5×T ²

Fig. 1 is used for explaining a figure being used for preferred melt viscosity P (T) scope that styrene/acrylic n-butyl multipolymer of the present invention (I) measures under 180-240 ℃ of temperature.In Fig. 1, the lower limit of the preferred melt viscosity scope of curve representation of drawing by solid line, wherein this lower limit is determined by following formula:

The lower limit of melt viscosity=1.46 * 10 ⁵-1119.2 * T+2.256 * T ²

The upper limit of melt viscosity=2.91 * 10 ⁵-2350 * T+5 * T ²

If melt viscosity P (T) is higher than the upper limit by above-mentioned equation definition, less FE often appears in the sheet material of being made by this styrene copolymer composite.On the other hand, if melt viscosity P (T) is lower than the lower limit by above-mentioned equation definition, bigger FE often appears in the sheet material of being made by this styrene copolymer composite.

In the present invention, the melt viscosity P (T) of styrene/acrylic n-butyl multipolymer (I) under 180-240 ℃ of temperature can use kapillary instrument (capirograph) (by Japanese Toyo Seiki company limited produce and market) to measure under the following conditions, its middle shear rate (SR) is 61/ second, capillary pipe length (L) is 10.0 millimeters, and capillary diameter (D) is that 1.00 millimeters and barrel diameter (B) are 9.50 millimeters.

For the storage modulus of styrene/acrylic n-butyl multipolymer (I), preferably, be 1.5 * 10 30 ℃ of storage moduluss of measuring down ⁹-2.5 * 10 ⁹Pa, and the temperature of this multipolymer (I) when relatively the storage modulus under 30 ℃ shows 50% storage modulus is 75-100 ℃.More preferably, be 1.7 * 10 30 ℃ of storage moduluss of measuring down ⁹-2.3 * 10 ⁹Pa, and the temperature of this multipolymer (I) when relatively the storage modulus under 30 ℃ shows 50% storage modulus is 75-85 ℃.

If styrene/acrylic n-butyl multipolymer (I) is lower than 1.5 * 10 30 ℃ of storage moduluss of measuring down ⁹Pa, the moulded products of being made by this styrene copolymer composite often improves deflection unsatisfactorily.On the other hand, if styrene/acrylic n-butyl multipolymer (I) surpasses 2.5 * 10 30 ℃ of storage moduluss of measuring down ⁹Pa, the moulded products of being made by this styrene copolymer composite often improves elongation at break unsatisfactorily.In addition, if the temperature of this multipolymer (I) when relatively the storage modulus 30 ℃ under shows 50% storage modulus is lower than 75 ℃, sheet material of making by this styrene copolymer composite or film often unsatisfactorily raising refractory at low temperatures melt cohesiveness.On the other hand, if the temperature when the relative storage modulus under 30 ℃ of this multipolymer (I) shows 50% storage modulus surpasses 100 ℃, the hot shrinkable films of being made by this styrene copolymer composite often improves unsatisfactorily at the hot contractility that hangs down under the heating temperature.

In the present invention, the storage modulus of styrene/acrylic n-butyl multipolymer (I) uses DMA983 (by U.S. DUPONT produce and market) to measure under the following conditions, and its medium frequency is that resonant frequency and temperature rise rate are 2 ℃/minute.

In the present invention, by the following various conditions that are used for producing the polymerisation process of multipolymer (I) of suitable adjusting, as the amount of vinylbenzene, n-butylacrylate and molecular weight regulator, raw material the residence time and polymeric reaction temperature, can control styrene/acrylic n-butyl multipolymer (I) in the melt viscosity P (T) under the 180-240 ℃ of temperature, the temperature of multipolymer (I) when 30 ℃ of relative storage moduluss under 30 ℃ with this multipolymer (I) of storage modulus of measuring down show 50% storage modulus at the polymeric kettle that is used for polyreaction.

Be used for styrene/acrylic n-butyl multipolymer of the present invention (I) and can pass through ordinary method, make as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization.

In order to improve the processibility of styrene copolymer composite, the melt flow rate (MFR) of styrene/acrylic n-butyl multipolymer (I) (following often be called " MFR ") is preferably 0.1-20 gram/10 minutes, more preferably the 1-10 gram is/10 minutes, measure under the defined terms " G " (temperature: 200 ℃, load: 5 kilograms) therein according to JISK-6870.

Below explain the asymmetric segmented copolymer (II) of the composition be used for first aspect and be used for the symmetrical segmented copolymer (II) of the composition of second aspect.

The asymmetric segmented copolymer (II) that is used for the composition of first aspect comprises the vinyl aromatic monomer unit of 65-90% weight and the conjugated diene monomeric unit of 35-10% weight.Asymmetric segmented copolymer (II) preferably comprises the vinyl aromatic monomer unit of 70-85% weight and the conjugated diene monomeric unit of 30-25% weight.

If be used for the conjugated diene monomeric unit that the asymmetric segmented copolymer (II) of the composition of first aspect comprises the vinyl aromatic monomer unit that is lower than 65% weight and surpasses 35% weight, the moulded products of being made by said composition has the FE of obvious appearance.On the other hand, if asymmetric segmented copolymer (II) comprises vinyl aromatic monomer unit that surpasses 90% weight and the conjugated diene monomeric unit that is lower than 10% weight, the elongation at break of the moulded products of being made by said composition is step-down unfriendly.

The symmetrical segmented copolymer (II) that is used for the composition of second aspect comprises the vinyl aromatic monomer unit of 75-85% weight and the conjugated diene monomeric unit of 25-15% weight.Symmetry segmented copolymer (II) preferably comprises the vinyl aromatic monomer unit of 77-83% weight and the conjugated diene monomeric unit of 23-17% weight.If be used for the conjugated diene monomeric unit that the symmetrical segmented copolymer (II) of the composition of second aspect comprises the vinyl aromatic monomer unit that is lower than 75% weight and surpasses 25% weight, the moulded products of being made by said composition has the FE of obvious appearance.On the other hand, if symmetrical segmented copolymer (II) comprises vinyl aromatic monomer unit that surpasses 85% weight and the conjugated diene monomeric unit that is lower than 15% weight, the elongation at break of the moulded products of being made by said composition is step-down unfriendly.

Be used for the asymmetric segmented copolymer (II) of composition of first aspect and the symmetrical segmented copolymer (II) that is used for the composition of second aspect and have a kind of block configuration respectively, wherein comprise polymer blocks that (A) at least two kinds of difference mainly are made up of vinyl aromatic monomer unit and (B) at least a vinyl-arene/conjugated diene copolymer block.In the present invention, term " the mainly polymer blocks of being made up of vinyl aromatic monomer unit " is meant that a kind of vinyl aromatic monomer unit content is 70% weight or higher polymer blocks, and term " vinyl-arene/conjugated diene copolymer block " is meant that a kind of vinyl aromatic monomer unit content is lower than the vinyl-arene of 70% weight/conjugated diene copolymer block.

As the asymmetric segmented copolymer (II) of the composition that is used for first aspect be used for the example of symmetrical segmented copolymer (II) of the composition of second aspect, can mention the linear block copolymers that has by the block configuration of following structural formula (1), (2) and (3) expression:

(1)A-(B-A) _n，

(2) A-(B-A) _n-B and

(3) B-(A-B) _N+1With

Have branched block multipolymer by the block configuration of following formula (4), (5), (6) and (7) expression:

(4)((A-B) _k) _m+2-X，

(5)((A-B) _k-A) _m+2-X，

(6) ((B-A) _k) _M+2-X and

(7)((B-A) _k-B) _m+2-X.

In with following formula (1)-(7), each A represents the main polymer blocks of being made by vinyl aromatic monomer unit independently; Each B represents vinyl-arene/conjugated diene copolymer block or conjugated diene homopolymers block independently; X is coupling agent such as silicon tetrachloride, tin tetrachloride, epoxy soybean oil, four glycidyl group-1, the two amino-ethyl hexanaphthenes of 3-, hydrocarbon polyhalogenide, carboxylicesters or the residue of many vinyl compounds or the residue of initiators for polymerization such as multifunctional organolithium compound; And n, k and m represent natural number respectively and are generally 1-5.

In the present invention, term " branched block multipolymer " is meant the segmented copolymer with a kind of like this structure, wherein a plurality of polymer chains are that the coupling agent of 3-8 or initiators for polymerization (as organic lithium compound) that functionality is 3-8 are keyed to together by a kind of functionality, and polymer chain is extended by the residue of coupling agent or the residue of initiators for polymerization like this.

Be used for the asymmetric segmented copolymer (II) of composition of first aspect and the symmetrical segmented copolymer (II) that is used for the composition of second aspect and can make by a kind of like this method respectively, therein ethylene base aromatic monomer and conjugate diene monomer be polymerization in the presence of as the organolithium compound of initiators for polymerization in hydrocarbon solvent.If segmented copolymer (II) is made by aforesaid method, reaction conditions is as follows.For the polyreaction that is used to produce segmented copolymer (II), temperature of reaction is generally-10 to 150 ℃, preferred 40-120 ℃.Polymerization reaction time changes according to other reaction conditions; But polymerization reaction time was generally 10 hours or lower, preferred 0.5-5 hour.Polyreaction is preferably carried out under rare gas element such as nitrogen atmosphere.Be not particularly limited polymerization pressure, keep liquid under monomer and the temperature of solvent in above-mentioned polymeric reaction temperature scope as long as this pressure is enough to make.In addition, must be carefully in case not only can the deactivation polymerisation catalysts and the impurity (as water, oxygen and carbon dioxide gas) of the reactive polymer that forming of deactivation invade polymerization reaction system.

Respectively in the composition aspect first and second, introduce terminal-modified dose residue by end, can improve the compatibility of styrene/acrylic n-butyl multipolymer (I) and segmented copolymer (II) with at least one polar group to segmented copolymer (II).As an example of terminal-modified dose, can mention terminal-modified dose: the polar group that (a) has active hydrogen with at least one polar group that is selected from following polar group (a)-(f); (b) has the polar group of nitrogen-atoms; (c) has the polar group of epoxide group or sulfo-epoxide group; (d) has the polar group of carbonyl or thiocarbonyl; (e) has the polar group of phosphorus atom; (f) have the polar group of the structural unit of representing by any one following formula structure:

-MX ₃,-MX ₂R ,-MXR ₂, and-MR ₃

Wherein M represents Si atom, Ge atom, Sn atom or Pb atom, and X represents halogen atom, and R represents alkyl, phenolic group or alkoxyl group.

If terminal-modified dose has polar group (f), at least two structural units with following formula structure are keyed jointing or separately be present in this terminal-modified dose mutually.Terminal-modified dose object lesson comprises having carbonyl, the compound of thiocarbonyl, acid halide, anhydride group, aldehyde group, sulfo-aldehyde group, carboxylate group, amide group, sulfonic acid group, phosphate group, bound phosphate groups, amino, imino-, nitrile group, pyridine group, quinoline group, epoxide group, sulfo-epoxide group, isocyanate groups or lsothiocyanates group, comprise the silicon compound of halogen atom and comprise the tin compound of halogen atom.Terminal-modified dose example more specifically comprises those that are described in careful Japanese patent application publication № 4-39495 (corresponding to United States Patent (USP) 5115035).

In the asymmetric segmented copolymer (II) of the composition of first aspect, respectively mainly (at least two kinds) polymer blocks (A) of being made up of vinyl aromatic monomer unit is included in the gel permeation chromatography of polymer blocks (A) and has the peak-peak molecular weight and have at least one at 30000-150000, the peak-peak polydispersity polymer block of the peak molecular weight in the preferred 30000-130000 scope, and the content of described peak-peak polydispersity polymer block in polymer blocks (A) is 20-50% weight, preferred 25-45% weight.If the peak molecular weight of peak-peak polydispersity polymer is lower than 30000, and/or the content of peak-peak polydispersity polymer block in polymer blocks (A) is lower than 20% weight, the deflection of the moulded products of making by said composition step-down unfriendly not only, and the fusing bonding often takes place at a lower temperature by the film that said composition is made.On the other hand, if the peak molecular weight of peak-peak polydispersity polymer block surpasses 150000, and/or the content of peak-peak polydispersity polymer block in polymer blocks (A) surpasses 50% weight, and 80 ℃ of contraction factors of the hot shrinkable films of being made by said composition and natural contraction factor be step-down unfriendly.

In the symmetrical segmented copolymer (II) of the composition of second aspect, (at least two kinds) polymer blocks (A) of mainly being made up of vinyl aromatic monomer unit comprises the polymer blocks with peak molecular weight respectively, described polymer blocks with peak molecular weight has at least one at 20000-70000 in the gel permeation chromatography of polymer blocks (A), peak molecular weight in the preferred 25000-65000 scope, and the described content of polymer blocks in polymer blocks (A) with peak molecular weight is 25-35% weight.If described peak molecular weight with polymer blocks of peak molecular weight is lower than 20000, and/or the described content of polymer blocks in polymer blocks (A) with peak molecular weight is lower than 25% weight, the deflection of the moulded products of making by said composition step-down unfriendly not only, and the fusing bonding often takes place at a lower temperature by the film that said composition is made.On the other hand, if described peak molecular weight with polymer blocks of peak molecular weight surpasses 70000, and/or the described content of polymer blocks in polymer blocks (A) with peak molecular weight surpasses 35% weight, and 80 ℃ of contraction factors of the hot shrinkable films of being made by said composition and natural contraction factor be step-down unfriendly.

Respectively for the polymer blocks (A) of the asymmetric block copolymer (II) in the first aspect composition and the symmetrical block copolymer (II) in the second aspect composition; The described peak molecular weight with polymer blocks (comprising peak-peak polydispersity polymer block) of peak molecular weight of polymer blocks (A) can be obtained by the molecular weight distribution of the polymer blocks that consists of polymer blocks (A), and the described content of polymer blocks in polymer blocks (A) with peak molecular weight can obtain with the amount of the vinyl aromatic monomer that forms polymer blocks (A) by being used for polymerisation.

If polymer blocks (A) is the vinyl-arene homopolymer block, the described peak molecular weight with polymer blocks of peak molecular weight of polymer blocks (A) also can be measured by the following method.At first, in the presence of as the perosmic anhydride of catalyzer, use t-butyl hydroperoxide that segmented copolymer (II) is carried out oxidative degradation, from segmented copolymer (II), isolate the vinyl aromatic polymer block like this, reclaim then gained vinyl aromatic polymer component (except mean polymerisation degree be about 30 or lower those) (referring to people's such as I.M.Kolthoff J.Polym.Sci.vol.1, p.426,1946).Gained vinyl aromatic polymer component is carried out GPC handle, obtain the GPC chromatogram.Then, use the calibration curve that is obtained by the GPC chromatogram with standard monodisperse polystyrene sample peak molecular weight, the peak molecular weight of this vinyl aromatic polymer component can be measured by any ordinary method (referring to for example Gel permeation chromatography, 1976, publish by Japanese Maruzen Co.Ltd.).

The peak molecular weight that polymer blocks (A) described has the polymer blocks of peak molecular weight can be used to form the catalyzer of vinyl aromatic polymer block and the amount of vinyl aromatic monomer is controlled by suitable adjusting.

As mentioned above, the described content of polymer blocks in polymer blocks (A) with peak molecular weight can be by the area ratio at the peak in the above-mentioned GPC chromatogram of vinyl aromatic polymer component gained, or by being used for polyreaction with the weight ratio of the amount of the vinyl aromatic monomer of the vinyl-arene homopolymer block that forms polymer blocks (A) and obtain.

Under the situation of asymmetric segmented copolymer (II) in the first aspect composition and the symmetrical segmented copolymer (II) in the second aspect composition, the polymer blocks of mainly being made up of vinyl aromatic monomer unit (A) has maximum weight polymer blocks and minimum weight polymer blocks respectively respectively.Below, the weight ratio of maximum weight polymer blocks and minimum weight polymer blocks often is called " maximum block/minimum block weight ratio ".

In the asymmetric segmented copolymer (II) of first aspect composition, the maximum weight polymer blocks of polymer blocks (A) is identical with the above-mentioned peak-peak polydispersity polymer block of polymer blocks (A).

In the polymer blocks (A) of the asymmetric segmented copolymer (II) that is used for the first aspect composition, maximum block/minimum block weight ratio is bigger.Specifically, maximum block/minimum block weight ratio is 1.2-4.5, preferred 1.5-4.0.Utilize this specific character, the moulded products of being made by the first aspect composition has excellent impact-resistance (as the surperficial resistance to impact shock of excellence), and is big slightly even the anisotropy of moulded products becomes.If maximum block/minimum block weight ratio is lower than 1.2, the impact-resistance of the moulded products of being made by said composition is step-down unfriendly.On the other hand, if maximum block/minimum block weight ratio surpasses 4.5, the transparency of the moulded products of being made by said composition is step-down unfriendly.

In the polymer blocks (A) of the symmetrical segmented copolymer (II) that is used for the second aspect composition, maximum block/minimum block weight ratio requires less.Specifically, to require be 1.0 to being lower than 1.2 to maximum block/minimum block weight ratio.Utilize this specific character, the moulded products of being made by said composition advantageously has little anisotropy.If maximum block/minimum block weight ratio is 1.2 or higher, will cause shortcoming, wherein the extrusion sheet of being made by said composition has big anisotropy, and therefore often splits extruding on the direction of sheet material.

Maximum block/minimum block weight ratio can be calculated with the monomeric amount that forms polymer blocks (A) by being used for polyreaction.If polymer blocks (A) is the vinyl-arene homopolymer block, maximum block/minimum block weight ratio also can (be obtained by aforesaid method by the vinyl aromatic polymer component, wherein in the presence of as the perosmic anhydride of catalyzer, use t-butyl hydroperoxide that segmented copolymer (II) is carried out oxidative degradation) area at gained GPC stratographic peak than and calculate, from segmented copolymer (II), isolate the vinyl aromatic polymer block like this, reclaim gained vinyl aromatic polymer component then.

As the example of the hydrocarbon solvent that is respectively applied for asymmetric segmented copolymer (II) in the production first aspect composition and the symmetrical segmented copolymer (II) in the second aspect composition, can mention aliphatic hydrocrbon such as butane, pentane, hexane, iso-pentane, heptane, octane and octane-iso; Alicyclic hydrocarbon such as pentamethylene, methylcyclopentane, hexanaphthene, methylcyclohexane and ethylcyclohexane; With aromatic hydrocarbons such as benzene, toluene, ethylbenzene and dimethylbenzene.These hydrocarbon solvents can separately or be used in combination.

Example as the vinyl aromatic monomer units that is respectively applied for asymmetric segmented copolymer (II) in the production first aspect composition and the symmetrical segmented copolymer (II) in the second aspect composition, can mention styrene monomer unit, o-methyl styrene monomeric unit, p-methylstyrene monomeric unit, to t-butyl styrene monomeric unit, 2,4-dimethyl styrene monomeric unit, α-Jia Jibenyixidanti unit, vinyl naphthalene monomeric unit, vinyl anthracene monomeric unit and 1,1-diphenylethylene monomeric unit.Wherein, the styrene monomer unit is particularly preferred.These vinyl aromatic monomer units can separately or be used in combination.

Example as the conjugated diene monomeric unit that is respectively applied for asymmetric segmented copolymer (II) in the production first aspect composition and the symmetrical segmented copolymer (II) in the second aspect composition, can mention 1,3-butadiene monomer unit, 2-methyl isophthalic acid, 3-divinyl (isoprene) monomeric unit, 2,3-dimethyl-1,3-butadiene monomer unit, 1,3-pentadiene monomeric unit and 1,3-hexadiene monomeric unit.These conjugated diene monomeric units can separately or be used in combination.Wherein, 1,3-butadiene monomeric unit and isoprene monomer unit are preferred.

In the composition of first aspect and second aspect, in order to suppress the appearance of FE effectively in the moulded products of being made by it, at least a portion conjugated diene monomeric unit in the segmented copolymer (II) is preferably isoprene monomer unit respectively.In this case, segmented copolymer (II) preferred package isoprene containing homopolymer block.

In addition, respectively in the composition of first aspect and second aspect, in order in the moulded products of making by it, to suppress the appearance of FE effectively, the aliphatic double bond of the conjugated diene monomeric unit in the segmented copolymer (II) is also preferably by partial hydrogenation, wherein the hydrogenation degree of aliphatic double bond is 1-50%, more advantageously 3-40%, the most advantageously 5-30%.

In the present invention, " hydrogenation degree " of the aliphatic double bond of the conjugated diene monomeric unit in the segmented copolymer (II) is meant hydrogenation and changes into the percentage ratio (%) of the aliphatic double bond of conjugated diene monomeric unit in the segmented copolymer (II) of stable hydrocarbon key, based on the sum of the aliphatic double bond of conjugated diene monomeric unit before hydrogenation in the segmented copolymer (II).

Hydrogenation degree can be measured by methods such as infrared (IR) spectrometer, nucleus magnetic resonance (NMR) devices.

As the example of the catalyzer that is used for hydrogenated block copolymer (II), can mention multiphase polymer and homogeneous polymer.

The object lesson of heterogeneous catalyst comprises the catalyzer of carrier carrying, comprises the metal (as Ni, Pt, Pd or Ru) that is carried on the carrier (as carbon, silica, alumina or diatomite).

The object lesson of homogeneous catalyst comprises so-called Ziegler type catalyzer, as comprises the organic acid salt of Ni, Co, Fe or Cr or the catalyzer of Acetyl Acetone salt and reductive agent (as organo-aluminium compound); So-called organometallic complex catalyzer, as comprise the organometallic compound of Ru, Rh or analogue; With the catalyzer that comprises cyclopentadiene titanium compound and reductive agent (as organic lithium compound, organo-aluminium compound or organo-magnesium compound).

Object lesson as the method for the aliphatic double bond of conjugated diene monomeric unit in the partial hydrogenation segmented copolymer (II), can mention being described in and examine Japanese patent application publication № 42-8704 (corresponding to AU6453173, CA815575 and DE1222260), examined Japanese patent application publication № 43-6636 (corresponding to United States Patent (USP) 3333024), examined the method for Japanese patent application publication № 63-4841 (corresponding to United States Patent (USP) 4501857) and careful Japanese patent application publication № 63-5401 (corresponding to United States Patent (USP) 4501857), wherein hydrogenation is carried out in inert solvent in the presence of hydrogenation catalyst respectively.In being described in the method for above-mentioned patent document, it is preferred being described in those that examine Japanese patent application publication № 63-4841 and 63-5401.

At the asymmetric segmented copolymer (II) that is used for the first aspect composition, the short chain section ratio of the vinyl aromatic monomer unit part of segmented copolymer (II) is a 1-25% weight, preferred 5-20% weight, wherein said short chain section ratio is defined as the weight percentage that comprises at least one vinyl aromatic monomer unit in the short chain section of being made up of 1-3 vinyl aromatic monomer unit, is base with the gross weight that is included in the vinyl aromatic monomer unit in the asymmetric segmented copolymer (II).If short chain section ratio is lower than 1% weight, the sheet material of being made by said composition or the elongation of film be step-down unfriendly.On the other hand, if short chain section ratio surpasses 25% weight, often cause shortcoming, wherein obviously distortion, i.e. the dimensional stability step-down of sheet material or film take place in sheet material or the film of being made by said composition when being heated.

At the symmetrical segmented copolymer (II) that is used for the second aspect composition, the short chain section ratio of the vinyl aromatic monomer unit of segmented copolymer (II) part is a 10-20% weight, and wherein said short chain section ratio is as above to the definition of the asymmetric segmented copolymer (II) that is used for the first aspect composition.If short chain section ratio is lower than 10% weight, the sheet material of being made by said composition or the elongation of film be step-down unfriendly.On the other hand, if short chain section ratio surpasses 20% weight, often cause shortcoming, wherein obviously distortion, i.e. the dimensional stability step-down of sheet material or film take place in sheet material or the film of being made by said composition when being heated.

The short chain section ratio of the vinyl aromatic monomer unit part of segmented copolymer can be measured by following method.Segmented copolymer is dissolved in the methylene dichloride.With gained solution ozone (O ₃) carry out oxidative degradation, obtain ozonide.The gained ozonide reduces in diethyl ether in the presence of lithium aluminum hydride, uses the pure water hydrolysis subsequently.Reclaim the vinyl-arene component by gains.The vinyl-arene component is carried out gel permeation chromatography (GPC), obtain the GPC chromatogram.By calculating the area ratio at the peak in the gained GPC chromatogram, obtain short chain section ratio (referring to " Koubunshi Gakkai Yokoushu (the polymer science society conference preprint collection) " of Yasuyuki Tanaka, Hisaya Sato and Yasunobu Nakafutami, 29 volumes, 2051 pages, 1980, Japan).

Respectively at the asymmetric segmented copolymer (II) that is used for the first aspect composition be used for the symmetrical segmented copolymer (II) of second aspect composition, the short chain section ratio of the vinyl aromatic monomer unit part of segmented copolymer (II) can by suitable adjusting carry out copolyreaction with generate the vinyl-arene/vinyl aromatic monomer of conjugated diene copolymer block and the amount of conjugate diene monomer in the segmented copolymer (II), carry out between the monomeric polymerisation reactivity of copolyreaction relation, etc. control.For example, the short chain ratio can carry out copolymerization by therein ethylene base aromatic monomer and conjugate diene monomer when its mixture is added polymerization reaction system continuously method, or control by therein ethylene base aromatic monomer and conjugate diene monomer carry out copolyreaction in the presence of polar compound or randomization reagent method.These methods can separately or be used in combination.

The example of polar compound or randomization reagent comprises ether such as tetrahydrofuran (THF), diglyme and diethylene glycol dibutyl ether; Amine such as triethylamine and tetramethylethylened; Thioether; Phosphine; Phosphamide; The salt of alkyl benzene sulphonate (ABS); With potassium alcoholate and sodium alkoxide.

The symmetrical segmented copolymer (II) that is used for the asymmetric segmented copolymer (II) of first aspect composition and is used for the second aspect composition has the number-average molecular weight of 10000-500000 respectively.The number-average molecular weight of segmented copolymer (II) can be used the calibration curve of standard monodisperse polystyrene sample gained, measures by GPC.

In the composition aspect first and second, in order to improve the processibility of composition, the MFR of segmented copolymer (II) is preferably 0.1-50 gram/10 minutes respectively, and more preferably the 1-20 gram is/10 minutes.

In the composition of first aspect, styrene/acrylic n-butyl multipolymer (I) is 10/90-90/10 with the weight ratio of asymmetric segmented copolymer (II), preferred 20/80-80/20.

If the amount of styrene/acrylic n-butyl multipolymer (I) surpasses 90% weight of the gross weight of styrene-based/n-butylacrylate multipolymer (I) and asymmetric segmented copolymer (II), the impact-resistance of the moulded products of being made by said composition is step-down unfriendly.On the other hand, if the amount of styrene/acrylic n-butyl multipolymer (I) is lower than 10% weight, the deflection of the moulded products of being made by said composition is step-down unfriendly.

In the composition of second aspect, styrene/acrylic n-butyl multipolymer (I) is 20/80-60/40 with the weight ratio of asymmetric segmented copolymer (II).

If the amount of styrene/acrylic n-butyl multipolymer (I) surpasses 60% weight of the gross weight of styrene-based/n-butylacrylate multipolymer (I) and symmetrical segmented copolymer (II), the impact-resistance of the moulded products of being made by said composition is step-down unfriendly.On the other hand, if the amount of styrene/acrylic n-butyl multipolymer (I) is lower than 20% weight, the deflection of the moulded products of being made by said composition is step-down unfriendly.

Respectively in the composition aspect first and second, the mist degree of the moulded products of being made by said composition is 1.2% or lower, more advantageously 1.0% or lower.If mist degree surpasses 1.2%, often cause shortcoming, for example, when said composition is used to produce film packaging or box (transparent container or box), the content of film packaging or box often manifests micro white when viewing film packing or box.

In the present invention, mist degree is measured as follows.Composition of the present invention uses sheet extruder or compressor to carry out molding, obtains the sheet material of 0.6 millimeter of thickness like this.Resulting sheet scribbles mineral oil.For resulting sheet, mist degree uses haze meter (CLOLR AND COLOR DIFFERENCE METER MODEL1001DP; By NIPPPN DENSHOKU KOGYO CO., LTD., Japan produce and market) measure.

As mentioned above, the moulded products of being made by styrene copolymer composite of the present invention does not have the obviously flake (FE) of appearance.The appearance of flake can be by adding vinylformic acid 2-(1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) ethyl)-4 in styrene copolymer composite of the present invention, 6-di-tert-pentyl-phenyl ester suppresses effectively as stablizer.The amount of stablizer is generally the 0.05-3 weight part, preferred 0.1-2 weight part, the styrene/acrylic n-butyl multipolymer (I) of relative 100 weight parts and the summation of segmented copolymer (II).If the amount of stablizer is lower than 0.05 weight part, can not suppresses FE satisfactorily and occur.On the other hand,, compare during with adding 0.05-3 weight part stablizer in styrene copolymer composite, can not improve and suppress the effect that FE occurs if the amount of stablizer surpasses 3 weight parts.

Styrene copolymer composite of the present invention also can comprise at least a phenol stabilizer of 0.05-3 weight part, the styrene/acrylic n-butyl multipolymer (I) of relative 100 weight parts and the summation of segmented copolymer (II).In addition, styrene copolymer composite of the present invention also can comprise at least a organophosphate or the organophosphite type stablizer of 0.05-3 weight part, the styrene/acrylic n-butyl multipolymer (I) of relative 100 weight parts and the summation of segmented copolymer (II).

The example of phenol stabilizer comprises propionic acid Octadecane base-3-(3, the 5-di-tert-butyl-hydroxy phenyl) ester, the vinylformic acid 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl ester, 2, ((octylsulfo) methyl)-(methylene radical-3-(3 for ortho-cresol, four for 4-two, the 5-di-tert-butyl-hydroxy phenyl) methane, 1 propionic ester), 3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene and 2,4-two (n-octyl sulfo-)-6-(4-hydroxyl-3,5-di-t-butyl phenylamino)-1,3, the 5-triazine.

The example of organophosphate or organophosphite type stablizer comprises tricresyl phosphite (nonyl phenyl) ester, 2,2-methylene radical two (4, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester, 2-((2,4,8,10-four (1, the 1-dimethyl ethyl) dibenzo (d, f) (1,3,2) oxygen base oxa-phosphepin-6-yl-two))-N, N-two-(2-((2,4,8,10-four (1, the 1-dimethyl ethyl) dibenzo (d, f) (1,3,2) oxygen ethyl oxa-phosphepin-6-yl-two)) ethamine and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester.

Styrene copolymer composite of the present invention can be by any ordinary method production.The example of these ordinary methods comprises that use generally is used for mixing tank such as opening rubber mixing machine, close mixed machine, Banbury mixer, the Ko-kneader of this area, has the melt-kneaded method of two-spool continuous kneader or forcing machine and wherein with every kind of components dissolved or be dispersed in the solvent and postheating is removed the method for solvent.

If desired, can in styrene copolymer composite of the present invention, add additive.The example of additive comprises polymeric additive, is 50% weight or lower vinyl-arene/conjugated diene block copolymer elastomerics, rubber-modified styrene copolymer, nonrubber modified styrene polymer and polyethylene terephthalate as therein ethylene base aromatic monomer unit content.

Other example of additive comprises those that are commonly used for plastics additive.The example of these additives comprises inorganic strengthening agent such as glass fibre, granulated glass sphere, silica, lime carbonate and talcum; Organic toughener such as organic fibre, tonka bean camphor-indene resin; Linking agent such as organic superoxide and inorganic peroxide; Pigment such as titanium white, carbon black and ferric oxide; Dyestuff; Fire retardant; Antioxidant; UV light absorber; Static inhibitor; Lubricant; Softening agent; Filler except that above-mentioned; And composition thereof.

Styrene copolymer composite of the present invention itself and all can carry out molding by the identical molds molding process that is used for molding ordinary hot plastic resin with the mixture of tinting material obtains being used for the moulded products of various application scenarios.For example, molding can be undertaken by injection moulding or blowing, obtains being used for parts, articles for daily use, food, odds and ends, the parts of photoelectric device and the container of analogue of office automation equipment.Especially, styrene copolymer composite of the present invention can be advantageously used in and produce hot shrinkable films, be used for the film of productive zone press mold and be used to produce the blister package of food and photoelectric device parts or the clear sheet of box.

Embodiment

Following according to embodiment and the present invention of Comparative Examples more detailed description, but they should not be construed as limiting the scope of the invention.

The various performance measurements of multipolymer that are used for following examples and Comparative Examples are as follows.

(1) melt viscosity:

The melt viscosity of multipolymer uses kapillary instrument (by Japanese Toyo Seiki company limited produce and market) to measure under the following conditions, and wherein shearing rate (SR) is 61 seconds ^-1, capillary pipe length (L) is 10.0 millimeters, capillary diameter (D) is that 1.00 millimeters and barrel diameter (B) are 9.50 millimeters.Time point in the temperature of this multipolymer that raises and when temperature reaches 180,190,200,210,220,230 and 240 ℃ is measured.

(2) storage modulus:

The storage modulus of multipolymer is measured as follows.Multipolymer is compression molded into thick about 3 millimeters and wide about 12 millimeters test sample.The gained test sample is fixed on two arms, and wherein the distance (span) between two arms is about 15 millimeters.Then, use the storage modulus of DMA983 (by U.S. DUPONT produce and market) at this test sample mensuration multipolymer under the following conditions, wherein temperature rise rate is 2 ℃/minute, and amplitude is 0.2 millimeter.

(3) melt flow (MFR):

MFR according to JISK-6870 therein the condition of defined " G " (temperature: 200 ℃, the load; 5 kilograms) measure down.

(4) hydrogenation degree:

The hydrogenation degree of multipolymer uses nucleus magnetic resonance (NMR) equipment (by the DPX-400 of German BRUCKER produce and market) to measure.

(5) the short chain section ratio in the vinyl aromatic monomer unit part of segmented copolymer (II) promptly, is included in the ratio of the vinyl aromatic monomer unit in the short chain section of being made up of 1-3 vinyl aromatic monomer unit:

With the speed of 150 ml/min ozone content 1.5% contained ozone (O ₃) oxygen add the solution of segmented copolymer in methylene dichloride to carry out the oxidative degradation of this segmented copolymer, obtain ozonide like this.The gained ozonide drops in the mixture of diethyl ether and lithium aluminum hydride, carries out the reduction of this ozonide like this.Then, in gains, drip pure water, add salt of wormwood then to salt out the vinyl-arene component to carry out the hydrolysis of this reduzate.The precipitation vinyl-arene single component of filtered and recycled gained.Should reclaim the vinyl-arene component and carry out gel permeation chromatography (GPC) processing, obtain the GPC chromatogram.By calculating the area ratio at the peak in gained GPC chromatogram, obtain short chain section ratio (referring to " Koubunshi Gakkai Yokoushu (the polymer science society conference preprint collection) " of Yasuyuki Tanaka, Hisaya Sato and Yasunobu Nakafutami, 29 volumes, 2051 pages, 1980, Japan).In above-mentioned oxidative degradation,, use ozonizer (by the OT-31R-2 of Japanese Nippon Ozone Co.Ltd. produce and market) as the device that is used to generate ozone.In GPC, use chloroform as solvent.GPC uses and (to observe) placed in-line Shimpack HSG-40H, Shimpack GPC-802 and Shimpack GPC-801 (respectively by Japanese Shiamadzu company produce and market) in this order carry out on the flow direction of solvent.

In addition, for sheet material that obtains in the following Examples and Comparative Examples or hot shrinkable films, carry out following assessment:

(1) tensile modulus (index that is used for deflection) and elongation at break:

Specimen for wide 12.7 millimeters sheet material (obtaining) form by extruding copolymer compositions, respectively at the extruding direction and measure perpendicular to this direction of extruding direction of sample, wherein the distance between the gauge length mark is 50 millimeters with the rate of extension of 5 mm/min.

(2) anisotropy

Will be in above (1) at sample extrude modulus in the tension values that direction obtains divided by the modulus in the tension values that in above (1), obtains at the direction of extruding direction perpendicular to this, assess the anisotropy of sheet material then according to the value that so obtains.Evaluation criteria is as follows:

Zero: be lower than 1.25

*: 1.25 or higher

(3) surperficial resistance to impact shock (index that is used for impact-resistance):

Measurement is carried out according to ASTMD-1709 under 23 ℃, and the diameter of different is weight is 1/2 inch, obtains 50% fracture value.

(4) mist degree:

Sheet surface is coated with whiteruss, measures the mist degree of sheet material then according to ASTM D1003.

(5) Vicat softening point (being used for stable on heating index)

Thick 0.6 a millimeter 7-8 sheet material is stacked into laminate mutually, then the gained laminate is carried out compression moulding, obtain the test sample of 3 millimeters of thickness.At the gained test sample, under 2 ℃/minute temperature rise rate, measuring Vicat softening point under 1 kilogram the load according to ASTM D-1525.

(6) 80 ℃ of contraction factors (index that is used for the hot contractility under low Heating temperature):

0.25 mm thick sheet material (obtaining by extruding copolymer compositions) is used 5 times of tenter machine uniaxial extensions on the direction of extruding direction perpendicular to sheet material, obtain the hot shrinkable films of the about 60 μ m of thickness like this.The hot shrinkable films of gained flooded 5 minutes in 80 ℃ hot water.Calculate 80 ℃ of contraction factors of this hot shrinkable films according to following formula:

80 ℃ of contraction factors (%)={ (L-L ₁)/L} * 100

Wherein L represents that this this hot shrinkable films impregnated in 80 ℃ of length before the hot water at it, and L ₁Represent this this hot shrinkable films length after it impregnated in hot water 5 minutes.

(7) natural contraction factor:

The hot shrinkable films that will obtain according to the same procedure of above (6) (have 40% 80 ℃ of contraction factors) left standstill under 35 ℃ 5 days, obtained " NS value " by following formula definition then:

NS value (%)={ (L ₂-L ₃)/L ₂} * 100

L wherein ₂And L ₃Represent that respectively this film is 35 ℃ of length of placing 5 days front and back down.

(8) in the melt resistant cohesiveness of hot water:

Corresponding being wound on the about respectively 8 centimetres vial of diameter of hot shrinkable films that will obtain according to the same procedure of above (6).Then, 3 vials are immersed in 85 ℃ the hot water and in hot water, left standstill 5 minutes, wherein these three vials are placed in the hot water so that these three vials are in contact with one another by this hot shrinkable films.Then, visual observation is twined the state of the film of these three vials, and according to the melt resistant cohesiveness of following criterion evaluation in hot water:

◎: these films do not melt bonding at all mutually.

Zero: the slight mutually fusing bonding of these films, so these films are separated from each other easily.

*: these films are firmly fusing bonding mutually, so these films are not easy to be separated from each other.

(9) flake (FE) (coccoid material):

Use 40 millimeters sheet extruders (that is, screw diameter is 40 millimeters the forcing machine that is used to produce sheet material) (under 235 ℃ extrusion temperature) to produce the sheet material of 0.3 millimeter of thickness in continuous 6 hours.The sheet material of making for the time point of 5 minutes and 6 hours after the beginning continuously moulding respectively severally goes out at per 300 centimetres ²The observed number that is of a size of 0.5 millimeter or higher FE on the sheet material.According to the difference on the FE number between two kinds of sheet materials, the appearance of following assessment FE:

Zero: this difference is lower than 50.

△: this difference is 50-100.

*: this difference surpasses 100.

The styrene/acrylic n-butyl copolymer A-1 that is used for following examples and Comparative Examples is produced as follows respectively to A-3.

In 10 liters of autoclaves being furnished with agitator, with 1 of 0.3 kilogram of ethylbenzene and predetermined amount, 1-two (t-butylperoxy) hexanaphthene (being used to regulate the MFR of the styrene/acrylic n-butyl multipolymer that will produce) adds simultaneously according to the vinylbenzene of the described weight ratio of table 1 and n-butylacrylate (wherein the total amount of vinylbenzene and n-butylacrylate is 5 kilograms).Under 110-150 ℃, carried out then polyreaction 2-10 hour.Use degassing extruder from resulting polymers, to remove unreacted monomer (that is, vinylbenzene, n-butylacrylate and ethylbenzene), obtain styrene/acrylic n-butyl multipolymer like this.

Table 1 has provided the performance of styrene/acrylic n-butyl copolymer A-1 to A-4.

The block copolymer B-1 that is used for following examples and Comparative Examples is produced as follows.

The 25% weight solution of 1,3-butadiene in hexanaphthene of in 30 liters of reactors of sealing, packing into and comprising 8 weight part 1,3-butadienes with chuck, the 0.055 weight part n-Butyl Lithium of in reactor, packing into then.The reactor nitrogen wash.First polyreaction was carried out under 80 ℃ 15 minutes, and keeping the pressure in the reactor simultaneously is 3-5kg/cm ²G.Then, the 25% weight solution of vinylbenzene in hexanaphthene that will comprise 21 parts by weight of styrene is once packed in this reactor, carries out second polyreaction 20 minutes under 80 ℃.Then, the 20% weight solution of 1,3-butadiene in hexanaphthene that will comprise 4 weight part 1,3-butadienes this reactor of once packing into carries out trimerization reaction 5 minutes under 80 ℃.Then, under 80 ℃, carry out the 4th polyreaction, in 25 minutes, in reactor, pack into the continuously simultaneously 1,3-butadiene that comprises 18 weight part 1,3-butadienes and 4 parts by weight of styrene and 20% weight ring hexane solution of cinnamic mixture.Then, the 20% weight solution of vinylbenzene in hexanaphthene that will comprise 45 parts by weight of styrene is once packed in this reactor, carries out the 5th polyreaction 35 minutes under 80 ℃.Then, methyl alcohol is packed in the reactor with the amount of 0.9 times of n-Butyl Lithium molar weight, and reactor content is stirred several minutes (1-5 minute), add stablizer subsequently.Then, from reactor, remove cyclohexane solvent, obtain the block copolymer B-1 of the composition forms of itself and stablizer.

In addition, the block copolymer B-2 that production has configuration shown in the table 2 is to B-14, and the polyreaction that wherein is used to form polymer blocks is carried out according to the same way as of producing branched block multipolymer B-1 basically.

Measure block copolymer B-2 all MFR to B-14, the result is in the scope of 5-10.

Embodiment 1-5 and Comparative Examples 1-6

Respectively in embodiment 1-5 and Comparative Examples 1-6, have the styrene copolymer composite of forming shown in the table 3 and under 200 ℃ extrusion temperature, use 40 millimeters sheet extruders to carry out extrusion molding, obtain thickness like this and be 0.25 millimeter sheet material.Measure tensile modulus (index that is used for deflection), elongation at break and the mist degree of this sheet material according to the method described above.In addition, the sheet material stretching is obtained hot shrinkable films.For the hot shrinkable films of gained, measure 80 ℃ of contraction factors (index that is used for the hot contractility under low Heating temperature), natural contraction factor according to the method described above and melt cohesiveness at the refractory of hot water.

In addition, produce the sheet material of 0.6 mm thick basically according to above-mentioned same way as, and measure surface impacts intensity (index that is used for impact-resistance) according to the method described above.

In addition, above-mentioned styrene copolymer composite used 40 millimeters sheet extruder continuous extrusions 6 hours under 235 ℃ extrusion temperature, obtained thickness like this and be 0.3 millimeter sheet material.For resulting sheet, assess FE according to the method described above.

Embodiment 6-9 and Comparative Examples 7-12

In embodiment 6-9 and Comparative Examples 7-12, use to have the styrene copolymer composite of forming shown in the table 4 respectively, produce sheet material and hot shrinkable films according to the same way as of embodiment 1 basically.For the sheet material and the hot shrinkable films of gained, measure 80 ℃ of contraction factors (index that is used for the hot contractility under low Heating temperature), natural contraction factor according to the method described above, melt cohesiveness and surface impacts intensity (index that is used for impact-resistance) at the refractory of hot water.In addition, calculate the anisotropy of sheet material according to the method described above.The result provides in table 4.

Embodiment 10

Block copolymer B-1 is carried out hydrogenation in the presence of the titaniferous hydrogenation catalyst that is described in careful Japanese patent application publication № 63-5401, like this with 1 in the block copolymer B-1, a part of aliphatic double bond hydrogenation of 3-butadiene monomer unit obtains hydrogenated block copolymer C-1 like this.For gained multipolymer C-1, the hydrogenation degree of aliphatic double bond is 12% weight.

Use comprises hydrogenated block copolymer C-1 and has the styrene copolymer composite of forming shown in the table 5, produces sheet material and hot shrinkable films according to the same way as of embodiment 1 basically.For resulting sheet and hot shrinkable films, measure and assess various performances.The result provides in table 5.

Embodiment 11

Block copolymer B-2 is carried out hydrogenation in the presence of the titaniferous hydrogenation catalyst that is described in careful Japanese patent application publication № 63-5401, like this with 1 in the block copolymer B-2, a part of aliphatic double bond hydrogenation of 3-butadiene monomer unit obtains hydrogenated block copolymer C-2 like this.For gained multipolymer C-2, the hydrogenation degree of aliphatic double bond is 42% weight.

Use comprises hydrogenated block copolymer C-2 and has the styrene copolymer composite of forming shown in the table 5, produces sheet material and hot shrinkable films according to the same way as of embodiment 1 basically.For resulting sheet and hot shrinkable films, measure and assess various performances.The result provides in table 5.

Embodiment 12

Basically repeat the step identical with production block copolymer B-1, different is just before adding methyl alcohol, to pack in the reactor as terminal-modified dose epoxidised soybean oil and carry out modification, and obtain so terminal-modified dose residue is keyed to segmented copolymer D-1 on its end with reactive terminal to the segmented copolymer chain that forming.This terminal-modified dose consumption and moles such as lithium atom as the n-Butyl Lithium of initiators for polymerization.

Use comprises gained segmented copolymer D-1 and has the styrene copolymer composite of forming shown in the table 5, produces sheet material and hot shrinkable films according to the same way as of embodiment 1 basically.For resulting sheet and hot shrinkable films, measure and assess various performances.The result provides in table 5.

Embodiment 13

Basically repeat the step identical with production block copolymer B-3, different is just before adding methyl alcohol, will be as terminal-modified dose four glycidyl group-1,3-diamino methylcyclohexane is packed in the reactor and to be carried out modification with the reactive terminal to the segmented copolymer chain that forming, obtains so terminal-modified dose residue is keyed to segmented copolymer D-3 on its end.This terminal-modified dose consumption and moles such as lithium atom as the n-Butyl Lithium of initiators for polymerization.

Use comprises gained segmented copolymer D-3 and has the styrene copolymer composite of forming shown in the table 5, produces sheet material and hot shrinkable films according to the same way as of embodiment 1 basically.For resulting sheet and hot shrinkable films, measure and assess various performances.The result provides in table 5.

Embodiment 14

Block copolymer B-6 is carried out hydrogenation in the presence of the titaniferous hydrogenation catalyst that is described in careful Japanese patent application publication № 63-5401, like this with 1 in the block copolymer B-6, a part of aliphatic double bond hydrogenation of 3-butadiene monomer unit obtains hydrogenated block copolymer C-6 like this.For gained multipolymer C-6, the hydrogenation degree of aliphatic double bond is 10% weight.

Use comprises hydrogenated block copolymer C-6 and has the styrene copolymer composite of forming shown in the table 6, produces sheet material and hot shrinkable films according to the same way as of embodiment 1 basically.For resulting sheet and hot shrinkable films, measure and assess various performances.The result provides in table 6.

Embodiment 15

Block copolymer B-7 is carried out hydrogenation in the presence of the titaniferous hydrogenation catalyst that is described in careful Japanese patent application publication № 63-5401, like this with 1 in the block copolymer B-7, a part of aliphatic double bond hydrogenation of 3-butadiene monomer unit obtains hydrogenated block copolymer C-7 like this.For gained multipolymer C-7, the hydrogenation degree of aliphatic double bond is 44% weight.

Use comprises hydrogenated block copolymer C-7 and has the styrene copolymer composite of forming shown in the table 6, produces sheet material and hot shrinkable films according to the same way as of embodiment 1 basically.For resulting sheet and hot shrinkable films, measure and assess various performances.The result provides in table 6.

Embodiment 16

Basically repeat the step identical with production block copolymer B-8, different is just before adding methyl alcohol, to pack in the reactor as terminal-modified dose epoxidised soybean oil and carry out modification, and obtain so terminal-modified dose residue is keyed to segmented copolymer D-8 on its end with reactive terminal to the segmented copolymer chain that forming.This terminal-modified dose consumption and moles such as lithium atom as the n-Butyl Lithium of initiators for polymerization.

Use comprises gained segmented copolymer D-8 and has the styrene copolymer composite of forming shown in the table 6, produces sheet material and hot shrinkable films according to the same way as of embodiment 1 basically.For resulting sheet and hot shrinkable films, measure and assess various performances.In addition, calculate the anisotropy of this sheet material according to the method described above.The result provides in table 6.

Embodiment 17

Basically repeat the step identical with production block copolymer B-6, different is just before adding methyl alcohol, will be as terminal-modified dose four glycidyl group-1,3-diamino methylcyclohexane is packed in the reactor and to be carried out modification with the reactive terminal to the segmented copolymer chain that forming, obtains so terminal-modified dose residue is keyed to segmented copolymer D-6 on its end.This terminal-modified dose consumption and moles such as lithium atom as the n-Butyl Lithium of initiators for polymerization.

Use comprises gained segmented copolymer D-6 and has the styrene copolymer composite of forming shown in the table 6, produces sheet material and hot shrinkable films according to the same way as of embodiment 1 basically.For resulting sheet and hot shrinkable films, measure and assess various performances.In addition, calculate the anisotropy of this sheet material according to the method described above.The result provides in table 6.

Table 5

(notes) stablizer a: vinylformic acid 2-(1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) ethyl)-4,6-di-tert-pentyl-phenyl ester

Stablizer b: propionic acid Octadecane base-3-(3, the 5-di-tert-butyl-hydroxy phenyl) ester

Stablizer c: tricresyl phosphite (nonyl phenyl) ester

* 1: the amount of styrene/acrylic n-butyl multipolymer and segmented copolymer is represented with % weight respectively, the gross weight of styrene-based/n-butylacrylate multipolymer and segmented copolymer.

* 2: the amount of stablizer is represented with weight part, the styrene/acrylic n-butyl multipolymer of relative 100 weight parts and the summation of segmented copolymer.

Table 6

Stablizer c: tricresyl phosphite (nonyl phenyl) ester

Industrial applicibility

The moulded products that is obtained by styrene copolymer composite of the present invention not only has high the stretching Modulus, high elongation at tear, the excellent transparency, the low natural shrinking factor and in hot water High refractory melt caking property, and do not have the flake that obviously occurs. In addition, by the present invention (said composition comprises asymmetric block copolymer as block copolymer to composition on the one hand (II)) moulded products that obtains have excellent surface impacts intensity (each of this moulded products to The opposite sex is slightly big); And (said composition comprises symmetrical block by the composition of second aspect present invention Copolymer is as block copolymer (II)) moulded products that obtains advantageously have low each to different The property. In addition, the hot shrinkable films that is obtained by the present composition does not only obviously occur Flake, and under low heating-up temperature, have excellent hot contractility. Therefore, this Bright composition can be advantageously used in produces various moulded products, such as wrap film be laminated to foam Film on the containers.

Claims

1. styrene copolymer composite comprises:

Wherein the vinyl aromatic monomer unit of segmented copolymer (II) partly has the short chain section ratio of 1-25% weight, wherein short chain section ratio is defined as the weight percentage that is included in the vinyl aromatic monomer unit at least a short chain section of being made up of 1-3 vinyl aromatic monomer unit, based on the gross weight that is included in the vinyl aromatic monomer unit in the described segmented copolymer (II)

Wherein said at least two kinds of polymer blocks (A) have maximum weight polymer blocks and minimum weight polymer blocks, and the weight ratio of wherein said maximum weight polymer blocks and described minimum weight polymer blocks is 1.2-4.5, and

Wherein said styrene/acrylic n-butyl multipolymer (I) is 10/90-90/10 with the weight ratio of described segmented copolymer (II).

2. according to the styrene copolymer composite of claim 1, wherein styrene/acrylic n-butyl multipolymer (I) comprises the styrene monomer unit of 83-89% weight and the n-butylacrylate monomeric unit of 17-11% weight.

3. according to the styrene copolymer composite of claim 1 or 2, it can access mist degree is 1.2% or lower moulded products.

4. according to any one styrene copolymer composite among the claim 1-3, the melt viscosity P (T) that wherein said styrene/acrylic n-butyl multipolymer (I) is measured under 180-240 ℃ temperature satisfies the following formula relation:

1.46×10 ⁵-1119.2×T+2.256×T ²≤P(T)≤2.91×10 ⁵-2350×T+5×T ²

5. according to any one styrene copolymer composite among the claim 1-4, wherein said styrene/acrylic n-butyl multipolymer (I) is 1.5 * 10 30 ℃ of storage moduluss of measuring down ⁹-2.5 * 10 ⁹Pa, and the temperature of wherein said multipolymer (I) when relatively the storage modulus under 30 ℃ shows 50% storage modulus is 75-100 ℃.

6. according to any one styrene copolymer composite among the claim 1-5, it also comprises 0.05-3 parts by weight of acrylic acid 2-(1-(the 2-hydroxyl-3 as stablizer, the 5-di-tert-pentyl-phenyl) ethyl)-4,6-di-tert-pentyl-phenyl ester, the described styrene/acrylic n-butyl multipolymer (I) of relative 100 weight parts and the summation of described segmented copolymer (II).

7. styrene copolymer composite comprises:

The vinyl aromatic monomer unit of wherein said segmented copolymer (II) partly has the short chain section ratio of 10-20% weight, wherein short chain section ratio is defined as the weight percentage that is included in the vinyl aromatic monomer unit at least a short chain section of being made up of 1-3 vinyl aromatic monomer unit, based on the gross weight that is included in the vinyl aromatic monomer unit in the segmented copolymer (II)

Wherein said at least two kinds of polymer blocks (A) have maximum weight polymer blocks and minimum weight polymer blocks, and the weight ratio of wherein said maximum weight polymer blocks and described minimum weight polymer blocks is 1.0 to being lower than 1.2, and

Wherein said styrene/acrylic n-butyl multipolymer (I) is 20/80-60/40 with the weight ratio of described segmented copolymer (II).

8. according to the styrene copolymer composite of claim 7, wherein said styrene/acrylic n-butyl multipolymer (I) comprises the styrene monomer unit of 83-89% weight and the n-butylacrylate monomeric unit of 17-11% weight.

9. according to the styrene copolymer composite of claim 7 or 8, it can access mist degree is 1.2% or lower moulded products.

10. according to any one styrene copolymer composite among the claim 7-9, the melt viscosity P (T) that wherein said styrene/acrylic n-butyl multipolymer (I) is measured under 180-240 ℃ temperature satisfies the following formula relation:

1.46×10 ⁵-1119.2×T+2.256×T ²≤P(T)≤2.91×10 ⁵-2350×T+5×T ²

11. according to any one styrene copolymer composite among the claim 7-10, wherein said styrene/acrylic n-butyl multipolymer (I) is 1.5 * 10 30 ℃ of storage moduluss of measuring down ⁹-2.5 * 10 ⁹Pa, and the temperature of wherein said multipolymer (I) when relatively the storage modulus under 30 ℃ shows 50% storage modulus is 75-100 ℃.

12. according to any one styrene copolymer composite among the claim 7-11, it also comprises 0.05-3 parts by weight of acrylic acid 2-(1-(the 2-hydroxyl-3 as stablizer, the 5-di-tert-pentyl-phenyl) ethyl)-4,6-di-tert-pentyl-phenyl ester, the described styrene/acrylic n-butyl multipolymer (I) of relative 100 weight parts and the summation of described segmented copolymer (II).