JPH04120152A - High nitrile-based polymer composition, molding and production thereof - Google Patents

Abstract

PURPOSE:To provide the subject composition having good thermally melt- flowability and thermal moldability even in the case of a high reduced viscosity and useful for films, etc., by homogeneously dispersing fine particles comprising a high nitrile copolymer in a matrix comprising a low nitrile copolymer. CONSTITUTION:The objective composition comprises (A) 50-97 pts.wt. of a polymer matrix of low nitrile copolymer comprising (i) polymer units of formula I (R<1> is H, methyl) and (ii) polymer units of formula II (R<2> is H, methyl; R<3> is 1-6C alkyl), the amount of the component i being 50-85wt.% based on the total amount of the polymer units, and (B) fine particles consisting of 1-20 pts.wt. of a synthetic rubber containing >=50% of 1, 3-conjugated diene units, 1-15 pts.wt. of a graft polymer (graft component) prepared by grafting a high nitrile copolymer comprising the component i or both the components i and ii to the synthetic rubber, the content of the component i being at least 86% based on the total amount of the components, and 1-15 pts.wt. of the high nitrile copolymer (non-graft component), the component B being homogeneously dispersed in the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a high nitrile copolymer 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 fluidity 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
The higher the content of the acrylonitrile component, the greater the value of 0, while such acrylonitrile resin
When heated to a temperature exceeding 0°C, cyclization occurs due to intramolecular condensation, causing coloration and infusibility.When the content of acrylonitrile component exceeds 85%, hot melt molding of acrylonitrile resin becomes virtually impossible. It becomes difficult.

Japanese Patent Publication No. 46-25005 discloses a method for producing a thermoplastic nitrile polymer having low gas permeability. This method uses (A) α such as acrylonitrile.
, a mixture of at least 70% by weight of a β-olefinically unsaturated mononitrile and (B) up to 30% by weight of an olefinically unsaturated carboxylic acid ester such as methyl acrylate10
0 parts by weight, (C) an emulsifier and radical polymerization initiation in an aqueous medium in the presence of 1 to 20 parts by weight of a copolymer of a conjugated diene selected from the group consisting of butadiene and isoprene and an olefinically unsaturated nitrile. In this method, polymerization is carried out at a temperature of 0 to 100° C. in the presence of a chemical agent and in the absence of molecular oxygen. The nitrile polymer produced by this method contains a copolymer of a conjugated diene and an olefinically unsaturated nitrile, as described above.

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. As the seed polymer, the same polymer as that described in the above-mentioned US Pat. No. 3,742,092 is used. 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.

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

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-proposed polymers and production methods are all characterized by a resin having a high content of unsaturated nitrile in the polymer, and are disclosed in Japanese Patent Publication No. 46-25005. , JP-A-48-62848 is aimed at imparting impact resistance and gas barrier properties by adding a rubber component and performing graft polymerization, while U.S. Patent No. 3.742.092 discloses a rubber component. The purpose is to add impact resistance and improve the polymerization rate by adding a seed polymer to perform graft polymerization, and U.S. Patent No. 3,732.336 also adds a seed polymer to improve the polymerization rate. This is for the purpose of improvement. Both methods are based on hot melt fluidity depending on the composition of the resin.

There is a problem that gas barrier properties and mechanical properties cannot be achieved in a well-balanced manner. Japanese Patent Publication No. 5,921,331 No. 9 JP-A-1-167318 aims at imparting solvent resistance by two-stage polymerization to create a compositional difference between a polymer grafted onto a rubber component and a matrix polymer. The balance between hot melt fluidity and gas barrier properties is unsatisfactory.

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 the present invention is to provide 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-mentioned composition of the present invention.

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

<Means for Solving the Problems> As a result of intensive research, the present inventors have determined that a low nitrile resin with high hot melt fluidity is used as a matrix polymer, and that the low hot melt fluidity is low or the low hot melt fluidity is low. 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 a polymerized unit (a) represented by (A) the following formula (a) 云CR2-Ch...(a)N, where R1 is hydrogen or a methyl group, and the following formula: (b) -(CH2-Chi)
...(b)0OR3 where R2 is hydrogen or a methyl group, and R3 is an alkyl group having 1 to 6 carbon atoms, and these polymerized units (
(B) 50 to 97 parts by weight of a polymer matrix of a low nitrile copolymer in which the proportion of polymerized units (a) is 50 to 85% by weight relative to the sum of a) and (b); 1.3 conjugated diene-containing synthetic rubber 1 to 20 parts by weight and the synthetic rubber consisting of the polymerized unit of the above formula (a), or the polymerized unit of the above formula (a) and the polymerized unit of the above formula (b) 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 (b). 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)
The ratio of polymerized units (a) to the total of
) is characterized by a large proportion of

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, expressed by the following formula % () where R1 is hydrogen or a methyl group. or monomer (a') and the following formula (b') COOR' where R1 is hydrogen or a methyl group, and R'' is an alkyl group having 1 to 6 carbon atoms. By graft polymerizing the monomer represented by
) and (b') to obtain a graft polymer-containing core layer polymer comprising a high nitrile copolymer in which the monomer (8') component accounts for at least 86% by weight, and (B) In the presence of the core layer polymer, the above formulas (a') and (
Monomer b') is polymerized to form monomers (a') and (b').
The ratio of the monomer (a') component to the total of the components is 50 to 8
This is a method for producing a polymer composition, characterized in that a shell layer polymer made of a low nitrile copolymer having a weight of 5% is obtained, and then (C) the core-shell type polymer particles described above are melt-molded.

The second method of the present invention is (A') In the production method according to claim 15, before the polymerization step (A) for obtaining the core layer polymer is completed, the above formula (
By adding monomers a') and (b') continuously or in portions and polymerizing, monomer (a') is added to the total of monomer (a') and (b') components. ) component ratio is 50-85
The polymer (a'
) obtain a core layer polymer having an intermediate layer having a large proportion of components, and (B') monomers of formulas (a') and (b') above in the presence of the core layer polymer having the intermediate layer. is polymerized to form a monomer (
A shell layer polymer consisting of a low nitrile copolymer in which the monomer (a') component accounts for 50 to 85% by weight with respect to the total of a') and (b') components is obtained, and then (a') The method is characterized in that the core-shell type multilayer polymer particles are melt-molded.

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,
Forms a sea-island structure. The composition 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 is derived from a core layer polymer containing synthetic rubber and a graft polymer. Originates from

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 also prevents problems during molding such as whitening and peeling during molding, and also has excellent dispersibility of fine particles.In particular, core-shell type multilayer particles with an intermediate layer have excellent adhesion between the core layer and shell layer. The adhesion is even better in the case of a gradient end type intermediate layer having a composition gradient in which 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 to the composition of the shell layer. In addition, hot melt fluidity and mechanical properties largely depend on the composition 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) and (b) are the above formula (a')
, Monomer (a') derived from monomer (b') is acrylonitrile or methacrylonitrile, of which acrylonitrile is preferred, and monomer (b') is alkyl acrylate or 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 methacrylic acid. Examples include hexyl. Among these, methyl acrylate is particularly preferred. Further, if necessary, less than 5% by weight of other copolymerizable monomers may be used, such as vinyl acetate and acrylamide.

Neutral monomers such as vinyl ethyl ether, vinyl chloride, vinylidene chloride, acrylic acid, 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, methacriconitrile, and 5-styrene are good.

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 initiation side, but there are no particular restrictions 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% by weight of polymerized units of. Further, 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 criteria. 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 content of units is small, and the polymerized unit (a) is contained in an amount of 50 to 85% by weight based on the total of polymerized units (a) and (b). Further, the low nitrile copolymer preferably contains the polymerized unit of the formula (a) in an amount of 65 to 80% by weight, more preferably 70 to 80% by weight 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, and the polymerization unit of the above formula (b) is a polymerization unit consisting of methyl acrylate. It is.

(11) The graft polymer accounts for 1 to 15% by weight of the composition, more preferably 2 to 13% by weight.

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

(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 dimethylformamide at 30°C.
The reduced viscosity measured in is in the range of 0.5 to 5 dJ/g, more preferably in the range of 0.5 to "ldit/g."

(vl) 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 unit (a) of the high nitrile copolymer is the polymerized unit (a) of the low nitrile copolymer of the matrix resin.
at least 2% by weight, more preferably at least 5% by weight, most preferably at least 1% by weight over the content of a)
0% more by weight.

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% of the polymerized units (a) from 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 commonly referred to as an emulsion graft method or a seed polymerization method. For example, in the presence of a rubber polymer, the proportion of the acrylonitrile component and/or methacrylonitrile component of the above formula (a) is 86% relative to the total amount of polymerized units of the above formulas (a) and (b).
Rubber component content 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 such that the rubber component content is ~100% by weight. Using the 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. First, seed polymerize the intermediate layer polymer made of a low nitrile copolymer with a small proportion of (a).The core layer polymer particles having 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 Seed polymerization is carried out by adding monomers in which the proportion of the monomer (a') component is smaller than the unreacted monomers to the place where the reaction monomers are present, either continuously or in portions. Next, using the core layer polymer particles having this intermediate layer as seeds,
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.
．． 1 to about 2% by weight.

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, a molecular weight regulator may or may not be used, and in the polymerization of the shell layer, it is preferable to use it at an appropriate concentration.The polymer emulsion obtained after emulsion polymerization is always Removal of unreacted monomers by
Coagulate, wash with water, dehydrate, dry, and add various stabilizers as necessary.
The composition of the present invention can be obtained by adding a pigment and the like and melt-extruding it into, for example, a pellet 7), or the powder can be directly molded.

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, calendar processing, and heat cent molding 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, a high nitrile copolymer cannot be stretched (at such a low stretching temperature, the film may become white).

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, thermoformability, 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 MI), seed polymer content, emulsion particle size, oxygen permeation amount, 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/d1, and the solution viscosity was measured at 30°C and found to be η1. Obtained by calculating /C.

・Conversion rate: 1 m of the emulsion obtained by polymerization
1 sample, diluted 10 times with water, put 20 μl 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: After thoroughly drying the sample, dissolve it in dimethyl sulfoxide and deuterated dimethyl sulfoxide and determine by IR and IH NMR.

・Ml: Zero conditions according to ASTM-D123B are temperature 200°C, load 12.5 kg, orifice diameter 2
．． Measured at 1 mmφ.

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

・Graft resin content: The sample was dissolved in acetonitrile/dimethylformamide (1:1), separated into a solvent-soluble resin component and a solvent-insoluble graft resin component, and further 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: Measured at a rotation speed of 700 rpm using an ultracentrifugal automatic particle size distribution analyzer CAPA-700 manufactured by Horiba, Ltd.

- Oxygen permeation rate: 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 can be modulated. control (Modern) Contrals) 0X- TRAN-100 type oxygen permeability meter using conditions of 30°C and 100% RH. Measured below.

- Bending properties: Using an injection molded sample piece, the bending elastic modulus 1 and bending strength were measured according to ASTM-D790.

- Film physical properties: The tensile strength and 1-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.

輼NIPOL-155110, 3 parts water
1 4 7.6 5 parts acrylonitrile
30.0 parts methyl acrylate
3.3 parts sodium persulfate
0.04 part ethylenediaminetetraacetic acid-potassium 0.0
4 parts 1 Monogen Y-1000, 64 parts (*I Nippon Zeon Co., Ltd., acrylonitrile-butadiene rubber latex, solid content 51%) (1 Daiichi Kogyo Seiyaku Co., Ltd., natural alcohol sulfate ester salt) Conversion rate at this time, polymer Physical properties such as composition were measured.

The results are shown in Table-1.

[Seed Polymerization] A mixture consisting of the following components was continuously added dropwise over a period of 3 hours to polymerize the intermediate layer).

water
8 2.0 5 parts acrylonitrile
50 parts methyl acrylate 16.
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 4 hours (polymerization of shell layer). The physical properties of the obtained emulsion, such as the conversion rate, are shown in Table 1. The residual monomer was removed from this emulsion, and the emulsion was salted out (coagulated) using aluminum sulfate to obtain a polymer powder.

Next, after sufficiently drying this polymer powder, it was extruded into a strand shape at 170° 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 carried out 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 It was carried out in the same manner as [Seed Polymerization]. The physical properties of the polymer at this time are shown in Table 1.

[Example 3] [Polymerization of core layer] The same procedure as in Example 1 was carried out except that the monomers were changed to 31.7 parts of acrylonitrile and 1.6 parts of methyl acrylate, and the physical properties of this polymer were shown in Table 1. .

[Seed Polymerization] Polymerization was carried out in the same manner as in Example 1 except that 48.3 parts of acrylonitrile and 18.4 parts of methyl acrylate were used. The physical properties of the polymer at this time are shown in Table 1.

[Example 4] [Polymerization of core layer] Polymerization was carried out in the same manner as in Example 1 [Polymerization of core layer], and the physical properties of this polymer are shown in Table-1.

[Seed Polymerization] Polymerization was carried out in the same manner as in Example 1 [Seed Polymerization] except that 55.3 parts of acrylonitrile and 11.4 parts of methyl acrylate were used to obtain a polymer. 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.
Polymerization was carried out for an hour.

NIPOL-155110, 3 parts water
1 4 7. 6 5 parts acrylonitrile
25 parts methyl acrylate
8.33 parts Sodium persulfate 0
．． 04 parts Ethylenediaminetetraacetic acid-potassium 0.04
Part: Monogen Y-1000, 64 parts: n-dodecylmercaptan: 1.1 parts The physical properties of the polymer are shown in Table 1.

[Seed Polymerization] A mixture consisting of the following components was added dropwise thereto over 3 hours.

water
8 2. 0 5 parts acrylonitrile
50 parts methyl acrylate
16.67 parts n-dodecyl mercaptan 2.
2 parts Sodium persulfate 0.0
2 parts Ethylenediaminetetraacetic acid-potassium 0.02 parts Monogen Y-1000, 36 parts After completing the dropwise addition, aging polymerization was further carried out at 60° C. for 4 hours. Table 1 shows the physical properties such as conversion rate of the emulsion obtained.
It was shown to. The same operation as in Example 1 was performed to obtain polymer chips. The physical properties of this polymer are shown in Table-1.

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

[Seed Polymerization] Comparative Example 1 It was carried out in the same manner as [Seed Polymerization]. The physical properties of the polymer at this time are shown in Table 1.

[Example 5] Flexural modulus of injection molding using the chip of Example 1.

A sample piece for measuring bending strength was obtained. In addition, a sheet with a thickness of 300 μm was produced by melt-forming at 180°C using an extruder equipped with a lower mold die, and this sheet molded product was stretched in both length and width using a tenter biaxial stretching machine at a stretching temperature of 105°C. A biaxially stretched film with a thickness of about 50 μm was obtained by simultaneously biaxially stretching in the direction of 0 bending elastic 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 a polymer was obtained in the same manner as in Comparative Example 1. 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 the drawing]

Figure 1.2.3 shows a schematic diagram of the core-shell type polymer particles of the present invention, where A and B are high nitrile copolymers of the core layer containing rubber and graft polymer, respectively. Shows the low nitrile copolymer of the shell layer. C and D indicate the low nitrile copolymer of the intermediate layer between the core layer and the shell layer, and the ANII composition in the polymer of C has a gradient from the composition of the core layer to the composition of the shell layer, and is close to the core layer. It has a moderately high nitrile composition. ANMi in the other polymer is an intermediate composition between the core layer and the shell layer and always has a constant composition. 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. The low nitrile copolymers (B, C, D) are shown below. 2. 3゜1990 Patent Application No. 241747 Name of the invention High nitrile polymer composition, molded article, and its relationship to the case of a person amending the manufacturing method Patent applicant address 17-4 Sumida 5-chome, Sumida-ku, Tokyo 〒534
Patent Department, Kanebo Co., Ltd., 1-5-90 Tomobuchi-cho, Bejima-ku, Osaka Telephone: (06) 921-1251 4. Date of amendment order Vol. Scope,” “Detailed Description of the Invention,” and “Brief Description of the Drawings.” Contents of the amendment (++ The scope of claims stated on pages 1 to 9 of the specification is amended as shown in the attached sheet. (2) The description of the description is amended as shown in the table below. 8゜One attached document listing the attached documents Above appended claim (1) (A) The following formula (a) 云CH, -Chi ... (a) N where R1 is hydrogen or a methyl group, the polymerized unit (a) represented by and the following formula (b) yun CH2-C juice
...(b) COOR" where R2 is hydrogen or a methyl group, and R3 is an alkyl group having 1 to 6 carbon atoms, and these polymerized units (a) and The ratio of polymerized unit (a) to the total of (b) is 5
(B) 1 to 20 parts by weight of a synthetic rubber containing 50% by weight or more of 1,3 conjugated diene in a polymer matrix of 0 to 85% by weight of a low nitrile copolymer; The 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 (b), and these polymerized units (
1 to 15 parts by weight of a high nitrile copolymer or a grafted polymer (graft component) in which the proportion of polymerized units (a) is at least 86% by weight based on the total of a) and (b), and a high nitrile copolymer (Non-grafted component) A high nitrile polymer composition characterized in that fine particles consisting of 1 to 15 parts by weight are 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 a high nitrile characterized in that the proportion of polymerized units (a) to the total of polymerized units (a) and (b) is 50 to 85% by weight, and the proportion of polymerized units (a) is larger than that of the polymer matrix. based polymer composition. (3) The polymer composition according to claim 2, wherein the proportion of polymerized units (a) in the intermediate layer is larger as it approaches fine particles of the high nitrile copolymer. (4) The polymer composition according to Claims 1 and 2, wherein the polymer unit of formula (a) forming a high nitrile copolymer is a polymer unit consisting of acrylonitrile. (5) The polymer composition according to Claims 1 and 2, wherein the polymer unit of formula (b) forming the high nitrile copolymer is a polymer unit consisting of methyl acrylate. (6) Claim 1, wherein the polymerization unit of the above formula (a) forming a low nitrile copolymer is a polymerization unit consisting of acrylonitrile, and the polymerization unit of the above formula (h) is a polymerization unit consisting of methyl acrylate. and the polymer composition according to item 2. (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 dA/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/lo minutes. (9) The polymer composition according to claim 1, wherein the content of polymerized units (a) of the high nitrile copolymer is at least 2% by weight greater than the content of polymerized units (a) of the low nitrile copolymer. thing. (10) The polymer composition according to claims 1 and 2, which is a diene-based synthetic rubber or 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, a monomer represented by the following formula (a') R N where R1 is hydrogen or a methyl group or monomer (a') and the following formula (b') COOR', where R2 is hydrogen or a methyl group, and R2 is an alkyl group having 1 to 6 carbon atoms. The monomer (a'
) and (b') to obtain a graft polymer-containing core layer polymer consisting of a high nitrile copolymer in which the monomer (a') component accounts for at least 86% by weight, and (B) In the presence of the core layer polymer, the above formulas (a') and (
Monomer b') is polymerized to form monomers (a') and (b').
The ratio of the monomer (a') component to the total of the components is 50 to 8.
A method for producing a polymer composition, which comprises obtaining a shell layer polymer consisting of a low nitrile copolymer accounting for 5% by weight, and then (C) melt-molding the core-soel type polymer particles. (16) (A') In the production method according to claim 15, before completing the polymerization step (A) for obtaining the core layer polymer,
By adding monomers of the above formulas (a') and (b') continuously or in portions and polymerizing, monomers (a') and (
The ratio of monomer (a') component to the total of b') component is 5
A core layer polymer having an intermediate layer containing 0 to 85% by weight and a larger proportion of the polymer (a') component than the shell layer polymer described below is obtained, and (B') a core layer polymer having the intermediate layer is obtained. The monomers of the above formulas (a') and (b') are polymerized in the presence of a polymer to form a monomer (
A shell layer polymer consisting of a low nitrile copolymer in which the monomer (a') component accounts for 50 to 85% by weight with respect to the total of a') and (b') components is obtained, and then (a' ) A method for producing a polymer composition, which comprises melt-molding the Co-L 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 (b') 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')
Claims 15 and 1, wherein the monomer is methyl acrylate.
A method for producing the polymer composition according to item 6. (20) Content of diene synthetic rubber or 1 of 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) Polymer composition in dimethylformamide, 30
17. A process 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 dA/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 of the polymer in the shell layer. A method for producing a polymer composition as described in .

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) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼... (b) Here, R^2 is hydrogen or a methyl group, and R^3 is an alkyl group having 1 to 6 carbon atoms. The polymer unit (a) is composed of a polymer unit represented by
(B) 1 to 20 parts by weight of a synthetic rubber containing 50 to 85% by weight of a 1,3 conjugated diene in a polymer matrix of a low nitrile copolymer in which the proportion of (B) is 50 to 85% by weight. and the synthetic rubber consists of polymerized units of the above formula (a) or the above formula (a)
and the polymerized unit of the above formula (b), and the polymerized unit (
Fine particles consisting of 1 to 15 parts by weight of a graft polymer grafted with a high nitrile copolymer having a proportion of at least 86% by weight and 1 to 15 parts by weight of a high nitrile copolymer are substantially uniformly dispersed. A high nitrile polymer composition characterized by: (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 a high nitrile characterized in that the ratio of polymerized units (a) to the total of polymerized units (a) and (b) is 50 to 85% by weight, and the ratio of polymerized units (a) is larger than that of the polymer matrix. based polymer 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 (b) forming the high nitrile copolymer is a polymerized unit consisting of methyl acrylate. (6) Claim 1, wherein the polymerized unit of the above formula (a) forming the low nitrile copolymer is a polymerized unit of acrylonitrile, and the polymerized unit of the above formula (b) is a polymerized unit of methyl acrylate. and the polymer composition according to item 2. (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') ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(a') Here , R^1 is hydrogen or a methyl group, or consists of monomers represented by (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 an alkyl group having 1 to 6 carbon atoms. ) and (b') for the total of monomer (a
') A graft polymer-containing core layer polymer made of a high nitrile copolymer in which the proportion of the component is at least 86% by weight is obtained, and (B) in the presence of the core layer polymer, the above formula (a') and (
Monomer b') is polymerized to form monomers (a') and (b').
The ratio of the monomer (a') component to the total of the components is 50 to 8
A method for producing a polymer composition, which comprises obtaining a shell layer polymer consisting of a low nitrile copolymer accounting for 5% by weight, 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, the monomers are added to the total of monomer (a') and (b') components. A core layer polymer having an intermediate layer in which the proportion of the component (a') accounts for 50 to 85% by weight and a proportion of the polymer (a') component in a larger proportion than the shell layer polymer described below is obtained, and (B') The monomers of formulas (a') and (b') above are polymerized in the presence of the core layer polymer having the intermediate layer to form the monomer (
A shell layer polymer consisting of a low nitrile copolymer in which the monomer (a') component accounts for 50 to 85% by weight with respect to the total of a') and (b') components is obtained, and then (c') A method for producing a polymer composition, comprising 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 (b') 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')
Claims 15 and 1, wherein the monomer is methyl acrylate.
A method for producing the polymer composition according to item 6. (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 .