JPH04120154A - High-nitrile-based polymer composition, molding and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject composition, excellent in hot-melt fluidity and hot molding processability even if the reduced viscosity is high by dispersing fine particles composed of a high-nitrile copolymer in a copolymer matrix of a low-nitrile copolymer. CONSTITUTION:The objective composition is obtained by homogeneously dispersing (B) fine particles composed of 1-20 pts.wt. synthetic rubber containing >=50wt.% 1,3-conjugated diene and 1-15 pts.wt. graft copolymer, composed of (i) polymerization units expressed by formula I (R<1> is H or methyl) or the component (i) and (iii) polymerization units expressed by formula III (R<4> is H or methyl; R<5> is 1-6C alkyl) and prepared by grafting a high-nitrile copolymer containing component (i) in an amount of at least 86wt.% based on the total amount of the components (i) and (iii) onto the aforementioned rubber and 1-15 pts.wt. high-nitrile copolymer in (A) 50-97 pts. wt. copolymer matrix of a low-nitrile copolymer composed of the component (i), (ii) polymerization units expressed by formula II (R<2> is H or methyl; R<3> is phenyl) and the component (iii). The amounts of the components in the low-nitrile copolymer are as follows. 50-85wt.% component (i), 15-40wt.% component (ii) and 0-10wt.% component (iii) based on the components (i) and (ii) or the total amount of the components (i), (ii) and (iii).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a high nitrile polymer composition, a molded article, and a method for producing the same. More specifically, the present invention relates to a novel high nitrile copolymer composition having excellent hot melt flowability and high gas barrier properties, a molded article, and a method for producing the same.

<Prior Art> Nitrile resins containing 50% or more of polymerized units of acrylonitrile or methacrylonitrile exhibit excellent gas barrier properties (gas impermeability) based on intermolecular bonds specific to nitrile groups. Resin is acid, alkali,
It has excellent chemical resistance to organic solvents and other mechanical properties such as flexural modulus, tensile strength, and creep resistance.
It is a well-balanced resin. Because of these many useful properties, nitrile resins are used in food packaging films.

Widely used as a material for sheets and containers.

On the other hand, in recent years, food preservation methods that do not add any additives such as antioxidants have been developed, and as a result, there is a desire to develop materials with even better gas barrier properties as food packaging materials, but there are technical difficulties. It's difficult.

For example, the gas barrier properties of acrylonitrile resin are -C
However, the higher the content of acrylonitrile component, the larger it becomes. On the other hand, such acrylonitrile resin has 20
When heated to a temperature exceeding 0°C, cyclization occurs due to intramolecular condensation, causing coloration and unmelting. When the content of acrylonitrile component exceeds 85%, hot melt molding of acrylonitrile resin becomes virtually impossible. It becomes difficult.

JP-A-48-62848 discloses a composition with low carbon dioxide permeability, which is composed of an acrylonitrile copolymer and a graft rubber.

U.S. Pat. No. 3,742,092 discloses at least 80 parts by weight of methacrylonitrile and 0 to 20 parts by weight of a monomer selected from methyl acrylate, methyl methacrylate and styrene. A process for producing impact resistant rubber-modified methacrylonitrile homo- or copolymers by polymerizing in the presence of 40 parts by weight of a preformed diene rubber, 5 to 160 parts by weight of a seed polymer, and a radical initiator. is disclosed. The seed polymer may be polymethacrylonitrile, a copolymer of methacrylonitrile with up to 20% by weight of other monovinyl monomers, polystyrene, polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile or acrylonitrile with other monovinyl monomers. It is a copolymer of

The rubber-modified methacrylonitrile homo or copolymer also includes:
As mentioned above, it is characterized by containing diene rubber.

U.S. Pat. No. 3,732,336 discloses at least 80 parts by weight of methacrylonitrile and 0 to 20 parts by weight of other monovinyl monomers, 5 to 160 parts by weight of a seed polymer and a radical initiator. polymerized in the presence of
A method for emulsifying methacrylonitrile homo- or copolymers is disclosed. The seed polymer used is the same as the seed polymer described in the above-mentioned US Pat. No. 3,742,092. Further, the above specification states that the polymerization rate is improved by the above production method, but the seed polymer is a high nitrile copolymer and the shell layer is a low nitrile copolymer. The preparation of the polymer particles is not specifically disclosed with data.

Japanese Patent Publication No. 59-21331 discloses that 80 to 95 parts by weight of a monomer such as acrylonitrile is graft-polymerized to 5 to 20 parts by weight of rubber, and the monomer grafted to the rubber is added to 100 parts by weight of the resulting polymer. Graft resin part 2 of polymer
40 parts by weight and the matrix resin portion of the monomer 40~
Compositions containing 93 parts by weight are disclosed.

JP-A-1-167318 discloses a high nitrile resin in which 60 to 99 parts by weight of a monomer mixture consisting of an unsaturated nitrile and an aromatic vinyl compound is grafted to 1 to 40 parts by weight of diene synthetic rubber. has been done.

<Problems to be Solved by the Invention> The above-mentioned chambered polymer and production method are both characterized by a resin having a high content of unsaturated nitrile in the polymer, and are disclosed in JP-A No. 48-62848. The purpose of the publication is to add a rubber component and carry out graft polymerization to impart impact resistance and gas barrier properties, while the specification of U.S. Patent No. 3,742,092 aims to add a rubber component and carry out graft polymerization, and The purpose of this is to add a seed polymer to impart impact resistance and improve the polymerization rate, and is disclosed in U.S. Patent No. 3.
．． No. 732.336 also aims to improve the polymerization rate by adding a seed polymer.

However, each method has the problem that it is not possible to achieve a good balance of hot melt fluidity, gas barrier properties, and mechanical properties with respect to the composition of the resin.

Japanese Patent Publication No. 59-21331, Japanese Patent Publication No. 1167318
The publication aims to provide solvent resistance by two-stage polymerization to create a composition difference between the polymer grafted onto the rubber component and the matrix polymer, but the balance between hot melt fluidity and gas barrier properties is insufficient. Not satisfied.

An object of the present invention is to provide a rubber-containing high nitrile polymer composition that has excellent hot melt fluidity and excellent gas barrier properties and mechanical properties, and a method for producing the same.

Still another object of the present invention is a film or sheet.

The object of this invention is to develop a high nitrile polymer composition that can be melt-molded into bottles, fibers, etc., and a method for producing the same.

Still another object of the present invention is to provide a high nitrile polymer molded article having the characteristics of the above composition of the present invention.

Further objects and advantages of the present invention will become apparent from the description below.

<Means for Solving the Problem> As a result of intensive research, the present inventors have found that, regarding nitrile resins, a low nitrile resin with high hot melt fluidity is used as a matrix polymer. By dispersing a high nitrile resin that exhibits no properties but has excellent gas barrier properties in the form of fine particles, new high nitrile compositions and molded products with an excellent balance of hot melt fluidity, gas barrier properties, and mechanical properties can be obtained. This heading led to the present invention.

That is, the first aspect of the present invention is (^) the following formula (a) R' published CHt-C? ... (a) N Here, R1 is hydrogen or a methyl group, and the polymerized unit (a) represented by the following formula (b) Ht - (CHt-C) ... (b) Here, R
1 is hydrogen or a methyl group, and R3 is a phenyl group, or the polymerized unit (a)
, (b) and the following formula (c) CH, -C)-...(C) consisting of polymerized units represented by COOR' and these polymerized units (
The proportion of the polymerized unit (a) is 50 to 85% by weight with respect to a) and (b) or the total of (a), (b), and (c).

(B) 50 to 97 parts by weight of a polymer matrix of a low nitrile copolymer in which the proportion of polymerized units (b) is 15 to 40% by weight and the proportion of polymerized units (c) is 0 to 10% by weight; 1 to 20 parts by weight of a synthetic rubber containing at least 1,3 conjugated diene in an amount of 1 to 20 parts by weight, and the synthetic rubber comprising polymerized units of the above formula (a), or polymerized units of the above formula (a) and the above formula (c). and these polymerized units (a)
, 1 to 15 parts by weight of a graft polymer grafted with a high nitrile copolymer in which the proportion of polymerized units (a) is at least 86% by weight, and 1 to 15 parts by weight of a high nitrile copolymer, based on the total of (c). The present invention provides a high nitrile polymer composition comprising fine particles substantially uniformly dispersed therein, and a molded article melt-molded from the polymer composition.

The second aspect of the present invention is that in the nitrile polymer composition according to claim 1, an intermediate layer exists between the polymer matrix and the fine particles of the high nitrile copolymer containing the rubber and the graft polymer. , the intermediate layer comprises polymerized units (a) and (b).
) or characterized in that the proportion of polymerized units (a) to the total of (a), (b), and (b) accounts for 50 to 85% by weight, and the proportion of polymerized units (a) is larger than that of the polymer matrix. do.

The first method of the present invention is (A) in the presence of a synthetic rubber containing 50% by weight or more of 1,3 conjugated diene.
) Here, R1 is hydrogen or a methyl group, or is composed of a monomer represented by monomer (a') and the following formula (C') CHt= C...(C') COOR" here , Rt is hydrogen or a methyl group, and R3 is an alkyl group having 1 to 6 carbon atoms.
A graft polymer-containing core layer polymer consisting of a high nitrile copolymer in which the proportion of the monomer (a') component is small (both 86% by weight) with respect to the total of components ) and (b') is obtained, and ( B) In the presence of the core layer polymer, the monomer of the above formula (a') and the following formula (b') Rt CH1= C... (b') where R1 is hydrogen or a methyl group; , and R3 is a phenyl group by polymerizing the monomers represented by (a') and (
b') or (a'), the ratio of monomer (a') component to the total of (b') and (a') components is 50 to 85% by weight
This is a method for producing a polymer composition, which is characterized in that a shell layer polymer made of a low nitrile copolymer is obtained, and then (C) the above-mentioned core-shell type polymer particles are melt-molded.

The second aspect of the method of the present invention is (8) In the production method according to claim 15, before the polymerization step (A) for obtaining the core layer polymer is completed, the above formula (a
By adding monomers (a') and (b') continuously or in portions and polymerizing them, monomers (a') and (b') or (a'), (b') and ( The monomer (a') component accounts for 50 to 85% by weight relative to the total of a') components,
In addition, a core layer polymer having an intermediate layer having a higher proportion of the polymer (a') component than the shell layer polymer described below is obtained, and (B') the above formula ( The monomers a') and (b') are polymerized, and the monomers (a') and (b') or the monomers (a'), (b') and (a') are A shell layer polymer made of a low nitrile copolymer in which the proportion of the polymer (a') component is 50 to 85% by weight is obtained, and then (a') the core-shell type multilayer polymer particles are melt-molded. shall be.

The composition of the present invention comprises a matrix made of a low nitrile copolymer, a fine particle multi-component polymer phase containing a synthetic rubber and a graft polymer, and made of a high nitrile copolymer,
The composition forming the sea-island structure is derived from polymer particles having a core-shell type multilayer structure, the matrix polymer is derived from a shell layer polymer, and the fine particle polymer contains synthetic rubber and a graft polymer. derived from the core layer polymer.

The characteristics of the present invention are that the graft polymer has good adhesion between the core layer and the high nitrile polymer, and due to the adhesion between the core layer and the shell layer, the adhesion between the matrix and the fine particles in the composition is good. It does not cause problems during molding such as whitening and flaking during molding, and also has excellent dispersibility of fine particles. In particular, core-shell type multilayer particles having an intermediate layer have excellent adhesion between the core layer and the shell layer, and the closer the intermediate layer is to the core layer, the closer the composition is to the core layer, and the closer the intermediate layer is to the shell layer, the closer the composition is to the shell layer. In the case of a gradient end type intermediate layer, the adhesion is even better. In addition, hot melt fluidity and mechanical properties largely depend on the molecular weight of the matrix in the composition, and gas barrier properties largely depend on the adhesion between the rubber component and high nitrile polymer in the composition and the composition of the fine particles. do.

The polymerized units of the above formulas (a), (b), and (c) are derived from the monomers of the above formulas (a'), (b'), and (c'), and the monomer (a') is acrylonitrile or methacrylate. Of these, acrylonitrile is preferred. Monomer (b') is styrene or α-methylstyrene,
Among these, styrene is preferred, and the monomer (a') is an alkyl acrylate or an alkyl methacrylate,
Examples include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate and hexyl methacrylate. etc. can be mentioned. Among these, methyl acrylate is particularly preferred, and if necessary, other copolymerizable monomers may be used in an amount of less than 5% by weight, such as 1, vinyl acetate, acrylamide, vinyl ethyl ether, Neutral monomers such as vinyl chloride and vinylidene chloride, acrylic acid, and methacrylic acid.

These include acidic monomers such as sulfonic acid and styrene sulfonic acid, and ammonium salts and metal salts of these monomers.

Furthermore, the synthetic rubber used in the present invention is a monomer having a conjugated diene, such as a homopolymer of 1,3-butadiene, isoprene, chloroprene, etc., a copolymer thereof, and at least one of these dienes and other monomers. For example, the conjugated diene monomer may be a copolymer with acrylonitrile, methacrylonitrile, styrene, methyl acrylate, methyl methacrylate, etc. Preferably, the conjugated diene monomer is 1,3-butadiene and isoprene, and the copolymerized monomer is Acrylonitrile, methacrylonitrile, and styrene are good materials.

Furthermore, the synthetic rubber used in the present invention preferably contains 50% by weight or more of a conjugated diene monomer, and is preferably manufactured by emulsion polymerization using a conventional radical initiator, but there is no particular restriction on the manufacturing method. . The content of synthetic rubber in the polymer composition is 1 to 20 parts by weight, preferably 2 to 15 parts by weight.
Parts by weight.

The graft polymer and high nitrile copolymer have the above formula (a
), or based on the sum of the polymerized units of the above formula (a) and the polymerized units of the above formula (b), the above formula (a)
Contains at least 86 1% by weight of polymerized units. In addition, the high nitrile copolymer preferably contains the polymerized units of formula (a) in an amount of 86 to 95% by weight, more preferably 87 to 92% by weight, based on the same standard. Similarly, the low nitrile copolymer of the matrix resin is composed of polymerized units of the above formulas (a) and (b), and the high nitrile copolymer containing the graft polymer in the composition has a high nitrile copolymer of the above formula (a). The low nitrile copolymer contains 50 to 85% by weight of the polymerized unit (a) based on the total of polymerized copolymers (a) and (b). It is preferable to contain 65 to 80% by weight, more preferably 70 to 80% by weight of polymerized units based on the same standard.

It is desirable that the polymer composition further satisfy at least one of the following relationships.

(i) The polymerization unit of the above formula (a) forming the high nitrile copolymer and the low nitrile copolymer is a polymerization unit consisting of acrylonitrile, the polymerization unit of the above formula (b) is styrene, and the polymerization unit of the above formula (c ) is a polymerized unit consisting of methyl acrylate.

(ii) the graft polymer is 1 to 15% by weight of the composition;
More preferably, it accounts for 2 to 13% by weight.

(Mountain) The high nitrile copolymer containing the graft polymer is 2 to 30% by weight of the polymer composition, more preferably 3 to 30% by weight of the polymer composition.
It accounts for 20% by weight.

(iv) The low nitrile copolymer accounts for 50 to 97% by weight of the composition, more preferably 65 to 95% by weight.

(V) Polymer composition in dimethylform 7amide at 30°C
The reduced viscosity measured in is in the range of 0.5 to 5 d 1/g, more preferably 0.5 to 2 d 17 g.

(1) The melt index value of the polymer composition at 200° C. is from 2 to 50 g/10 minutes, more preferably from 3 to 25 g/10 minutes.

(vi) The content of the polymerized units (a) of the high nitrile copolymer is lower than the polymerized units (a) of the low nitrile copolymer of the matrix resin.
), more preferably at least 5% by weight, most preferably at least 10% by weight than the content of
There are many doublets.

The intermediate layer existing between the matrix and the fine particles of the high nitrile copolymer or the core layer polymer and the shell layer polymer in the composition has a ratio of polymerized units (a) to the total of polymerized units (a) and (b). occupies 50 to 85% by weight, and the polymeric unit (a) is less than the polymer matrix or shell layer polymer.
A large proportion of Preferably the proportion of polymerized units (a) is 65
It is contained in an amount of up to 80% by weight, more preferably in an amount of 70 to 80% by weight.

The intermediate layer may have a uniform composition or a composition with a concentration gradient, but preferably the proportion of polymerized units (a) increases as it approaches the fine particles or core layer polymer in the composition.

The composition of the present invention can be produced by a method generally referred to as an emulsion grafting method or a seed polymerization method. However, based on the total amount of polymerized units of formulas (a) and (b) above, 86 to
Containing a rubber component obtained by emulsion graft polymerization of monomers consisting of the above formula (a') or represented by the above formulas (a') and (b') in an aqueous medium with a weight of 100% Using the high nitrile copolymer as a seed, the shell layer is then polymerized by emulsion polymerization in an aqueous medium.

The method for forming core-shell type multilayer particles having an intermediate layer is to first polymerize core layer polymer particles made of a high nitrile copolymer in the presence of a rubber polymer, and then use the particles as seeds to form polymerized units from the core layer polymer. The intermediate layer polymer made of a low nitrile copolymer with a small proportion of (a) is seed-polymerized.The core layer polymer particles containing this intermediate layer are used as seeds to further polymerize units ( It is obtained by seed polymerizing a shell layer polymer made of a low nitrile copolymer having a small proportion of a). Polymerized unit (a) of intermediate layer
A method for forming core-shell type multilayer particles having a composition gradient where the ratio of Next, seed polymerization is carried out by adding monomers in which the proportion of monomer (a') component is smaller than that of unreacted monomers to the place where the reaction monomer is present, either continuously or in portions. Using core layer polymer particles having an intermediate layer as a seed,
It is obtained by seed polymerizing a shell layer polymer made of a low nitrile copolymer having a lower proportion of polymerized units (a) than the intermediate layer polymer.

The method of controlling the thickness, content, or composition gradient of the intermediate layer is to control the amount of polymerization in the intermediate layer polymerization process, or to control the amount of polymerization in the core layer polymerization process where unreacted monomers exist.
Furthermore, this can be done by controlling the addition rate or addition time when continuously adding the monomer. Monomer is supplied all at once and added in 3 parts.

Continuous addition can be adopted, but continuous addition is preferable in order to carry out seed polymerization effectively.

As the emulsifier, known anionic emulsifiers, cationic emulsifiers, and nonionic emulsifiers can be appropriately selected and used. Emulsifier concentration is important in seeded polymerization and is approximately 0 in the polymerization system.
．． Forms 1 to about 2% overlay.

It is not preferable to use too much or too little emulsifier.

Too much will generate new polymer particles and reduce the efficiency of seed polymerization. On the other hand, if it is too small, emulsion stability will decrease and cause aggregation. It is preferable to add the emulsifier continuously.0 As the polymerization initiator, a known polymerization initiator can be used, and as the molecular weight regulator, mercaptans and the like can be used.

In the polymerization of the core layer containing the rubber polymer, the molecule I! PI knots may or may not be used, but it is preferable to use them at an appropriate concentration in the shell layer polymerization. The composition of the present invention can be obtained by processing the composition into, for example, pellets by dehydrating, drying, adding various stabilizers, pigments, etc. as necessary, and melt-extruding the composition.Also, the composition of the present invention can be directly molded into powder.

The polymer composition of the present invention is preferably obtained from core-shell multilayer polymer particles of the method of the present invention, as described above.
In addition, for example, it can also be produced by mixing an emulsion of a high nitrile copolymer and an emulsion of the low nitrile copolymer produced separately and treating the same as above, but stretching after molding may cause whitening, breakage, etc. Cheap.

The composition obtained according to the present invention can be easily melt-molded by known molding methods such as extrusion molding, injection molding, blow molding, and inflation molding.

For example, it can be processed into primary molded products such as films, sheets, and containers. Further heating, uniaxial stretching, simultaneous biaxial stretching, successive 2
Secondary forming such as axial stretching, compression molding, vacuum forming, calendering, and heat setting is also possible. In this case, known molding machines can be used. Depending on the purpose, a matting agent 1
There is no problem in adding colorants, heat stabilizers, ultraviolet absorbers, etc. during molding.

The melt-molded molded article of the present invention has a sea-island two-phase structure in which a high nitrile copolymer is an island component and a low nitrile copolymer is a sea component. A high nitrile copolymer has a high nitrile copolymer dispersed in a polymer matrix of a low nitrile polymer in the form of a long elongate shape in one direction or a shape spread in a planar shape by stretching or the like. It is preferred in terms of exhibiting good gas barrier properties, and particularly preferred when the molded product is a stretched film or a stretched bottle.

The stretching temperature at the time of stretching is preferably a temperature at which the high nitrile copolymer is easily deformed, and requires a temperature higher than the glass transition point of the nitrile copolymer, which is at least as low as possible. Even if the stretching temperature is such that a low nitrile copolymer is easily stretched, the film will whiten if the stretching temperature is low such that a high nitrile copolymer is difficult to stretch.

Although problems such as breakage occur, a nearly transparent film can be obtained under appropriate stretching conditions.

The molded product of the present invention has superior bending strength and film bowing elongation compared to homogeneous copolymers of the same composition made by conventional methods, and has other mechanical properties such as strength, impact resistance, transparency, heat resistance, It also has excellent chemical resistance. That is, the composition of the present invention has good processability such as melt moldability, aging shapeability, and stretchability, and can be used as food packaging films, containers, and containers for drugs and cosmetics.

<Examples> The present invention will be explained below with reference to Examples. All "parts" and "%" in the examples are based on weight.

The reduced viscosity, conversion rate, polymer composition ratio, melt index (hereinafter abbreviated as M+), seed polymer content, emulsion particle size, oxygen permeation amount 1 bending physical properties, and film physical properties were measured according to the following methods.

・Reduced viscosity: After thoroughly drying the sample, it was dissolved in N-N dimethylformamide (hereinafter abbreviated as DMF) to a concentration of 0.4 g/dl, and the solution viscosity was measured at 30°C. Obtained from the calculation of C.

・The emulsion obtained by conversion polymerization is 1 m
1 sample, diluted 10 times with water, put 20 μr into a vial, vaporized at 120° C., and charged the headspace gas into a gas chromatograph (GC-9A, manufactured by Shimadzu Corporation) to calculate the residual monomer.

The conversion rate is a percentage of the total amount of monomer charged. Represents remer conversion rate.

-Polymer composition ratio: After thoroughly drying the sample, it is dissolved in dimethyl sulfoxide and heavy dimethyl sulfoxide, and determined by IR and 1H NMR.

・Ml: 6 conditions according to ASTM-D1238 are temperature 200°C, load 12.5 kg, orifice diameter 2
．． Measured at 1 mmφ.

- High nitrile resin content Calculated from second seed polymer (core layer polymer) and final conversion rate.

- Graft resin-containing M: The sample was separated into a solvent-soluble resin component and a solvent-insoluble graft resin component in an acetonitrile/dimethylformamide vessel, and then centrifuged at 12.00 rpm for 20 minutes. The content of each is determined by calculation from the amount of rubber charged and the conversion rate of the total polymer.

・Average particle size: Manufactured by Horiba, Ltd. The measurement was performed using an ultracentrifugal automatic particle size distribution analyzer CAPA-700 at a rotational speed of 700 rpm.

- Excess amount of oxygen i3: After sufficiently drying the sample (powder), it was extruded at 170°C using a melt extruder and pelletized using a pelletizer. This chip is melt-molded at 180°C to create a sheet. This sheet molded product was biaxially stretched to obtain a measurement film.

Using this film, the amount of oxygen permeation was measured using an OX-TRAN-100 oxygen permeability meter manufactured by Modern Controls.
Measurement was carried out under the conditions of 0°C and 100% RH.

・Bending properties: bending elastic modulus using injection molded sample pieces. Bending strength was measured according to ASTM-D790.

- Film physical properties: The tensile strength and tensile elongation of the biaxially stretched film in each direction were measured according to ASTM-D 638.

[Example 1] [Polymerization of core layer] A mixture consisting of the following components was charged into a stainless steel reactor, and after sufficiently purging the inside of the reactor with nitrogen, the mixture was heated at 60°C for 1 hour with stirring.
Polymerization was carried out for an hour.

"NIPOL-155110, 3 parts water
1 4 7. 6 5 parts acrylonitrile
30.0 parts methyl acrylate
3.3 parts sodium persulfate 0
．． 04 parts Ethylenediaminetetraacetic acid-potassium 0.04
Part 1 Monogen Y -1000,64 parts (*I Nippon Zeon Co., Ltd. Acrylonitrile-butadiene rubber latex Solid content 51% Average particle size 0.18 μm
) ("2 Daiichi Kogyo Seiyaku Co., Ltd., natural alcohol sulfate ester salt) [Seed polymerization] A mixture consisting of the following components was continuously dropped therein over 3 hours (polymerization of the intermediate layer).

water
8 2. 0 5 parts acrylonitrile
50 parts styrene 1
6.67 parts n-dodecyl mercaptan 2.5
0.02 parts Sodium persulfate 0.02 parts Ethylenediaminetetraacetic acid-potassium 36 parts Monogen Y-1000 After completing the dropwise addition, polymerization was further carried out at 60° C. for 1 hour. The physical properties of the obtained emulsion, such as the conversion rate, are shown in Table 1. Residual monomers were removed from this emulsion, and the emulsion was salted out using aluminum sulfate (
coagulation) to obtain a polymer powder.

Next, after sufficiently drying this polymer powder, it was extruded into a strand shape at 190° C. using a melt extruder, and pelletized using a pelletizer. The physical properties of this polymer (polymer composition) are shown in Table 1.

[Example 2] [Polymerization of core layer] The same procedure as in Example 1 [Polymerization of core layer] was performed except that NIPOL-1551 was changed to 21.8 parts, and the physical properties of this polymer are shown in Table 1.

[Seed Polymerization] Example 1 [The same operation as in Seed Polymerization was performed, and the physical properties of this polymer are shown in Table 1.

[Example 3] [Polymerization of the core layer] Same as Example 1 [Polymerization of the core layer] except that the ingredients for [polymerization of the core layer] were 31.7 parts of acrylonitrile and 1.6 parts of methyl acrylate. The physical properties of this polymer are shown in Table 1.

[Seed polymerization] Example 1 [Seed polymerization] Example 1 except that the charges for [seed polymerization] were 46.67 parts of acrylonitrile and 20 parts of styrene.
Seed polymerization] was performed, and the physical properties of this polymer C are shown in Table 1.

[Example 4] [Polymerization of core layer] Example 1 [Polymerization of core layer] The same procedure as in Example 1 [Polymerization of core layer] was carried out except that the polymerization time was 1.5 hours.

[Seed polymerization] Example 1 Polymerization was carried out in the same manner as in [Seed polymerization],
The physical properties of this polymer are shown in Table-1.

[Comparative Example 1] [Polymerization of core layer] A mixture consisting of the following components was charged into a stainless steel reactor, and after sufficiently purging the inside of the reactor with nitrogen, the mixture was heated at 60°C with stirring for 1 hour.
Time polymerization was performed.

NIPOL-155110, 3 parts water
1 4 7. 6 5 parts acrylonitrile
10 parts styrene
1.11 parts Sodium persulfate 0
．． 04 parts Ethylenediaminetetraacetic acid-potassium 0.04
Part Monogen Y - 1000, 64 parts The physical properties of the polymer at this time are shown in Table 1.

[Seed Polymerization Example 1] The same operation as in [Seed Polymerization] was performed, and the physical properties of this polymer are shown in Table 1.

[Comparative Example 2] [Polymerization of core layer] Same as Example 1 [Polymerization of core layer] except that 23.3 parts of acrylonitrile and 10.0 parts of methyl acrylate were used in [Polymerization of core layer] The physical properties of this polymer are shown in Table 1.

[Seed polymerization Example 1 Example 1 except that the charges for [seed polymerization] were 53.3 parts of acrylonitrile and 13.3 parts of styrene.
The same operation as [seed polymerization] was performed, and the chips of [Example 5] were injection molded using the chips of Example 1 to determine the flexural modulus.

A sample piece for bending strength measurement was obtained. In addition, a sheet with a thickness of 300 am was created by melt-forming at 180°C using an extruder with a T-shaped die, and this sheet molded product was stretched vertically and horizontally at a stretching temperature of 105°C using a tenter biaxial stretching machine. 2 simultaneously in each direction of
A biaxially stretched film with a thickness of about 50 μm was obtained by axial stretching.
Flexural modulus.

The bending strength and tensile strength and elongation of the film were measured. The results are shown in Table-2.

[Comparative Example 3] The same procedure as in Example 5 was carried out except that the polymer was obtained in the same manner as in Comparative Example 2. The results are shown in Table 2 (Effects of the Invention) As described above, the nitrile polymer compositions and molded products have good hot melt fluidity and thermoforming processability even in the range where the nitrile content in the polymer is high and the reduced viscosity is high. It has excellent gas barrier properties, tensile elongation of the film, and bending strength of the molded product, making it extremely useful in practice. Furthermore, the method of the present invention is industrially easy and extremely useful in practice.

[Brief explanation of drawings]

Figure 1.2.3 shows a schematic diagram of the core-shell type polymer particles of the present invention, and A and B respectively show a high nitrile copolymer in the core layer containing rubber and a low nitrile copolymer in the shell layer. , C, and D indicate the low nitrile copolymer in the intermediate layer between the core layer and the shell layer, and the ANI composition in the polymer of C has a gradient from the composition of the core layer to the composition of the shell layer. The closer it is, the higher the nitrile composition. The AN composition in the other polymer is an intermediate composition between the core layer and the shell layer, and is always constant. Figure 4.5 shows a composition or molded article melt-molded from core-shell type polymer particles, where A is the high nitrile copolymer consisting of the core layer containing the above-mentioned rubber, and B' is the above-mentioned intermediate layer and shell layer. A low nitrile copolymer (B, C, D) consisting of
shows. Figure Figure Figure Figure Procedure Shinbo Seisho March 19, 1991

Claims (25)

[Claims] (1) (A) The following formula (a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (a) Here, R^1 is hydrogen or a methyl group, and the polymerized unit (a) represented by The following formula (b)▲There are mathematical formulas, chemical formulas, tables, etc.▼...(b) Here, R^2 is hydrogen or a methyl group, and R^
3 is a phenyl group, or consists of polymerized units represented by (a), (b) and the following formula (c) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (c) unit, and the ratio of polymerized unit (a) to the total of these polymerized units (a) and (b) or (a), (b) and (c) is 50 to 85% by weight, and the polymerized unit (b) ) proportion is 15 to 40% by weight and polymerized units (c
) in 50 to 97 parts by weight of a polymer matrix of a low nitrile copolymer in which the proportion of (B) is 0 to 10% by weight, 1 to 20 parts by weight of a synthetic rubber containing 50% by weight or more of 1,3 conjugated diene; and the synthetic rubber consists of a polymerized unit of the above formula (a), or consists of a polymerized unit of the above formula (a) and a polymerized unit of the above formula (c), and these polymerized units (a)
From 1 to 15 parts by weight of a graft polymer grafted with a high nitrile copolymer in which the proportion of polymerized units (a) is at least 86% by weight based on the total of (c) and 1 to 15 parts by weight of a high nitrile copolymer. A high nitrile polymer composition comprising fine particles substantially uniformly dispersed. (2) In the high nitrile polymer composition according to claim 1, an intermediate layer exists between the polymer matrix and the fine particles of the high nitrile copolymer containing rubber and a graft polymer, and the intermediate layer is polymerized unit (a) and (b) or (a)
, a high nitrile polymer characterized in that the ratio of polymerized units (a) to the total of (b) and (c) is 50 to 85% by weight, and the ratio of polymerized units (a) is larger than that of the polymer matrix. Coalescing composition. (3) The polymer composition according to claim 2, wherein the proportion of polymerized units (a) in the intermediate layer increases as it approaches fine particles of the high nitrile copolymer. (4) The polymer composition according to Claims 1 and 2, wherein the polymerized unit of the formula (a) forming the high nitrile copolymer is a polymerized unit consisting of acrylonitrile. (5) The polymer composition according to Claims 1 and 2, wherein the polymerized unit of the formula (c) forming the high nitrile copolymer is a polymerized unit consisting of methyl acrylate. (6) The polymerization unit of the above formula (a) forming the low nitrile copolymer is a polymerization unit consisting of acrylonitrile, the polymerization unit of the above formula (b) is a polymerization unit consisting of styrene, and the polymerization unit of the above formula (c) is a polymerization unit consisting of styrene. The polymer composition according to claims 1 and 2, wherein the polymerized unit is methyl acrylate. (7) Polymer composition in dimethylformamide at 30°C
The polymer composition according to claims 1 and 2, which has a reduced viscosity in the range of 0.5 to 5 dl/g. (8) The melt index value of the polymer composition is 2 to 50
Polymer compositions according to claims 1 and 2 in the range of g/10 minutes. (9) The polymer composition according to claim 1, wherein the content of polymerized units (a) in the high nitrile copolymer is at least 2% by weight greater than the content of polymerized units (a) in the low nitrile copolymer. thing. (10) The polymer composition according to claims 1 and 2, wherein the diene-based synthetic rubber is an acrylonitrile-butadiene copolymer. (11) A molded article melt-molded from the polymer composition according to claims 1 and 2. (12) The molded article according to claim 11, wherein the molded article is a film, sheet, or container. (13) The molded article according to claim 11, wherein the molded article is a film and is at least uniaxially stretched. (14) The molded article according to claim 11, wherein the content of polymerized units (a) in the high nitrile copolymer is at least 2% by weight greater than the content of polymerized units (a) in the low nitrile copolymer. (15) (A) In the presence of a synthetic rubber containing 50% by weight or more of 1,3 conjugated diene, the following formula (a') ▲ Numerical formula, chemical formula, table, etc. ▼... (a
') Here, R^1 is hydrogen or a methyl group, or consists of monomers represented by (a') and the following formula (c') ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ...(c') Here, R^2 is hydrogen or a methyl group, and R^
3 is an alkyl group having 1 to 6 carbon atoms. By graft polymerizing the monomers represented by
') A graft polymer-containing core layer polymer made of a high nitrile copolymer having a proportion of at least 86% by weight is obtained, and (8) in the presence of the core layer polymer, the above formula (
Monomer of a') and the following formula (b') ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(b') Here, R^2 is hydrogen or a methyl group, and R^
3 is a phenyl group by polymerizing the monomer represented by
The proportion of monomer (a') component is 50 to 85% by weight relative to the total of monomers (a') and (b') or (a'), (b') and (c') components. A method for producing a polymer composition, which comprises obtaining a shell layer polymer made of a low nitrile copolymer, and then (C) melt-molding the core-shell type polymer particles. (16) (A') In the production method according to claim 15, before the polymerization step (A) for obtaining the core layer polymer is completed,
By adding monomers of the above formulas (a') and (b') continuously or in portions and polymerizing, monomers (a') and (b') or (a'), (b The ratio of monomer (a') component to the total of components ') and (c') is 50 to 85% by weight.
, and in the presence of (B') the core layer polymer having the intermediate layer, The monomers of formulas (a') and (b') above are polymerized to form monomers (a') and (b') or (a'), (b') and (
The ratio of monomer (a') component to the total of c') component is 5
A method for producing a polymer composition, which comprises obtaining a shell layer polymer consisting of a low nitrile copolymer accounting for 0 to 85% by weight, and then (c') melt-molding the core-shell type multilayer polymer particles. (17) The method for producing a polymer composition according to items 15 and 16, wherein the monomer of formula (a') forming the polymer of the core layer is acrylonitrile. (18) The method for producing a polymer composition according to items 15 and 16, wherein the monomer of formula (c') forming the polymer of the core layer is methyl acrylate. (19) The monomer of the above formula (a') forming the polymer of the shell layer is acrylonitrile, and the monomer of the above formula (b')
The method for producing a polymer composition according to claims 15 and 16, wherein the monomer of formula (b') is methyl acrylate and the monomer of formula (b') is styrene. (20) The content of diene-based synthetic rubber is 1 in the polymer composition.
17. Process for producing a polymer composition according to claims 15 and 16, comprising ~20% by weight. (21) The content of the graft polymer is 1 to 1 in the polymer composition.
Process for producing a polymer composition according to claims 15 and 16, comprising 15% by weight. (22) The method for producing a polymer composition according to claims 15 and 16, wherein the high nitrile copolymer of the core layer containing the graft polymer accounts for 2 to 30% by weight of the polymer composition. (23) The polymer composition was dissolved in dimethylformamide at 30%
The method for producing a polymer composition according to claims 15 and 16, wherein the reduced viscosity measured at °C is in the range of 0.5 to 5 dl/g. (24) The melt index value of the polymer composition is 2 to 5
A process for producing a polymer composition according to claims 15 and 16, in the range of 0 g/10 minutes. (25) Claim 15, wherein the content of the monomer (a') component in the polymer of the core layer is at least 2% by weight greater than the content of the monomer (a') component in the polymer of the shell layer. A method for producing a polymer composition as described in .