JPH03115347A - Resin composition - Google Patents

Abstract

PURPOSE:To prepare a high-nitrile resin compsn. having improved adhesive properties and excellent gas barrier properties without deteriorating the transparency by compounding specified amts. of a metal salt of a fatty acid and a specific phosphorus compd. into a high-nitrile resin. CONSTITUTION:100 pts.wt. high-nitrile resin (e.g. a butadiene-acrylonitrile copolymer) is compounded with 0.01-1 pt.wt. metal salt of a fatty acid (e.g. calcium stearate or magnesium stearate) and 0.01-1 pt.wt. compd. of the formula [wherein X and Y are each alkyl, halogen, etc.; and R is an alkyl group of CnH2n+1 (wherein n is 1-20)] (e.g. 9,10-dihydro-9-phosphor-10-oxaphenanthrene-9-oxide).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a high nitrile resin composition that has good transparency and excellent thermal stability during molding.

[Prior Art] High nitrile resins are resins with excellent gas barrier properties against oxygen, nitrogen, carbon dioxide, and the like.

This high nitrile resin is generally extruded or injection molded in the same way as other thermoplastic resins by adding phenolic, phosphorus, or sulfur stabilizers.

Molding processes such as blow molding are possible.

However, with the above high nitrile resin, extrusion molding,
In injection molding, blow molding, etc., if molding is continued for a long time, resin may adhere to and accumulate on the die, inside the extruder, on parts of the screw, etc., and this may deteriorate and cause burns.

On the other hand, metal salts of fatty acids are disclosed in, for example, JP-A No. 49-345
47, it is known to improve the processability and thermal stability of acrylonitrile-based polymers, and when added to high nitrile resins, it also improves the adhesion of the resin to dies, etc. can be improved.

In addition, the phosphorus compound represented by formula (1) is, for example, an acrylonitrile-styrene copolymer or an acrylonitrile-styrene-phtadiene copolymer, as described in Japanese Patent Publication No. 4B-38220 and Japanese Patent Publication No. 49-351. It is known as a discoloration inhibitor during processing of copolymers containing acrylonitrile.

[Problems to be Solved by the Invention] However, when a metal salt of a fatty acid is added to a high nitrile resin, as the amount added increases, the adhesion is improved and scorch is reduced, but the scorch becomes noticeable during processing. If the amount of the metal salt of a fatty acid added is increased to such a level that the amount of the metal salt of the fatty acid is increased, the problem arises that the transparency of the resin decreases, and one of the characteristics of the high nitrile resin, which is good transparency, is lost.

Furthermore, if molding is continued under conditions where scorch is likely to occur, the gas barrier property, which is a characteristic of high nitrile resins, will be impaired.

Means for Solving Problem F] As a result of intensive studies to solve the above problems, the present inventors have found that the transparency can be greatly increased by using the following phosphorus compounds in addition to fatty acid metal salts. The present invention was achieved by discovering that the adhesion can be improved without any damage and the gas barrier properties of the molded product can be maintained.

That is, the present invention provides 0.01 to 1 part by weight of fatty acid metal salt and general formula (
This is a high nitrile resin composition containing 0.01 to 1 part by weight of the phosphorus compound represented by 1).

[However, X and Y are an alkyl group, a halogen group, a halogenated alkyl group, an OH group, an amino group, a nitro group,
ROM group, RNH group, RNO group, COOR group, OR group,
Or indicates a hydrogen atom. Note that R is CnH2n+1
It represents an alkyl group (n=1 to 20), an alkylene group of CnH2n, or an aryl group. ] The high nitrile resin used in the present invention is a copolymer mainly composed of unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile, and has 50 unsaturated nitrile compound units.
It contains at least 55% by weight, preferably at least 55% by weight.

As the comonomer to be copolymerized with the unsaturated nitrile compound, any unsaturated compound that can be copolymerized with the above-mentioned unsaturated nitrile compound can be used, such as styrene, pucdiene, isoprene, methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. Examples include acrylates, and one or more of these are copolymerized with an unsaturated nitrile compound.

In addition, as a high nitrile resin, rubbery copolymers such as butadiene-acrylonitrile copolymer, butadiene-styrene copolymer, isoprene-styrene copolymer, polybutadiene, polyisoprene, etc. are mixed so as to form the unsaturated nitrile units mentioned above. Examples include those obtained by copolymerizing a mixture of an unsaturated nitrile compound and the above-mentioned comonomer in the presence of these rubbery copolymers, which are preferred because they have impact resistance.

Further, as the high nitrile resin, the above-mentioned rubber-like resin has a matrix of a copolymer of an unsaturated nitrile compound and the above-mentioned comonomer, and has a graft part having the same composition as the matrix or a graft part that is compatible with the matrix. A mixture with a copolymer may also be used.

These high nitrile resins contain antioxidants, ultraviolet absorbers, antistatic agents, lubricants, and inorganic fillers.

It does not matter if it contains a coloring pigment or a small amount of other resin.

The fatty acid metal salts used in the present invention are sodium, calcium, and magnesium salts of higher fatty acids such as oleic acid, stearic acid, and valmitic acid.

It is a salt with metals such as zinc and aluminum. Among these, calcium stearate and magnesium stearate are preferred.

As the phosphorus compound represented by formula (1), 9,10-dihydro-9-phosphor-10-oxaphenanthrene-9-oxide or derivatives thereof having various substituents as described above are used, such as 1. 3-Ditert-butyl-9,0-dihydro-9-phosphor-10oxaphenanthrene-9-oxide, 3-ditert-butyl-9,10-dihydro-9-phosphor-10oxaphenanthrene-9- Oxide is used.

In the present invention, by using a metal salt of a fatty acid and a phosphorus compound represented by (1) in combination with the above-mentioned high nitrile resin, the adhesion of the resin during molding is improved, and molding with good transparency is achieved. However, if the amount of the fatty acid metal salt added is less than 0.05 part by weight, a sufficient adhesion improvement effect cannot be obtained. Further, if the amount of the metal salt of fatty acid added is more than 1 part by weight, it is not preferable because, for example, resin pressure fluctuation occurs in extrusion molding, etc., impairing molding stability.

On the other hand, the compound represented by formula (1) is added in an amount of 0.
If the amount is less than 0.5 parts by weight, the effect of improving transparency will be poor, and if it is more than 1 part by weight, the resin will clearly turn yellow, which is not preferable.

Although the method for producing the resin composition of the present invention is not particularly limited,
For example, high nitrile resin, fatty acid metal salt and formula (1)
A method is used in which a predetermined amount of the compound represented by (1) and, if necessary, other additives are mixed in a high-speed rotating mixer and then melted and kneaded through an extruder to form pellets.

It can also be obtained by preparing a masterbatch containing a fatty acid metal salt and a compound represented by formula (1) together or individually based on a nitrile resin and blending these with a high nitrile resin.

Furthermore, when polymerizing a high nitrile resin, it is particularly preferable to add and mix these compounds at the end of the polymerization, since the dispersibility will be improved and the effects of the present invention can be achieved even with a small amount of addition.

[Example] Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 High nitrile resin obtained by polymerizing 100 parts by weight of a mixture consisting of 75 parts by weight of acrylonitrile and 25 parts by weight of methyl acrylate in the presence of 10 parts by weight of butadiene-acrylonitrile rubbery copolymer (70% by weight of butadiene) Calcium stearate, which is a fatty acid metal salt, and 9.10-dihydro-9
- Phosphor-10-oxaphenanthrene-9-oxide HCA (trade name, manufactured by Sangen Kagaku ■) was added in the amounts shown in Table 1, and mixed with a Henshil mixer. High nitrile resin pellets were obtained by extrusion using an extruder with a diameter of 30 mm at a resin temperature of about 200'C.

This pellet was molded using an injection molding machine FS manufactured by Nissei Jushi Kogyo Co., Ltd.
A test piece with a thickness of 2 mm was prepared using 80S12ASE. Using this test piece, haze was measured using a haze meter TC-H1ll manufactured by Tokyo Juishiki ■.

In addition, the high nitrile resin pellets were passed through an extruder with a diameter of 30 mm, and the extruder temperature was adjusted to C11 from the hopper side.
210°C, C21220°C, C3: 230°C and die: 230°C, about 30 to 4
Pelletization extrusion was performed at a high setting of 0°C and a screw rotation speed of 6 ORPM, and after 8 hours, the extruder was immediately disassembled and cleaned to confirm whether the resin could be peeled off from the metal surface of the screw etc. to the container. .

The results are shown in Table 1.

Furthermore, a film with a thickness of 0.03 mm was made using the pellets obtained in 4 to 8 hours in the above experiment, and the oxygen permeation rate of the obtained film was measured and found to be 10 cc/%.
・It was 24 hours at Ill.

Comparative Example 1 Haze measurement and peelability rII evaluation were carried out in the same manner as in Example 1 except that fatty acid metal salt and HCA or HCA were not added.

The results are shown in Table 1.

Example 2 0.3 parts by weight of magnesium stearate, which is a fatty acid metal salt, and HC were added to the same high nitrile resin powder as in Example 1.
Ao and 1 part by weight were mixed and pelletized in the same manner as in Example 1 to obtain high nitrile resin pellets.

Using this pellet, the haze value was measured and the releasability was confirmed in the same manner as in Example 1.

The results are shown in Table 1.

Comparative Example 2 Example 2 except that HCA was not added.
Measurement of haze value and releasability of TIN in the same manner as in 1.
confirmed.

The results are shown in Table 1.

Example 3 As a high nitrile resin, 100 parts by weight of a mixture consisting of 80 parts by weight of acrylonitrile, 5 parts by weight of methyl methacrylate and 15 parts by weight of styrene was polymerized to 8 parts by weight of a butadiene-acrylonitrile rubbery copolymer (70 parts by weight of butadiene). Using the powder of high nitrile resin (acrylonitrile content 73%, according to nitrogen analysis) obtained in Example 1, high nitrile resin was prepared in the same manner as in Example 1 except that 0.3 parts by weight of calcium stearate and 3 parts by weight of HCAo were added. A nitrile resin pellet was obtained.

Using this pellet, the haze value was measured in the same manner as in Example 1, and the releasability was confirmed.

The results are shown in Table 1.

Comparative Example 3 The haze value was measured and the releasability was confirmed in the same manner as in Example 3 except that HCA was not added.

The results are shown in Table 1.

Comparative Example 4 A high nitrile resin pellet was obtained in the same manner as in Example 3 except that 0.3 parts by weight of HCA was added.

Using this pellet, the haze value was measured in the same manner as in Example 1, and the releasability was confirmed.

The results are shown in Table 1.

When the oxygen permeation rate was measured by the method shown in Example 1 using the pellets obtained in the experiments of Comparative Examples 1 and 4, it was 15 to 20 cc/g・24 hr・atm, and the pellets used for measurement were Minute burnt material was observed on the film.

Example 4 The resin used in Example 1 was polymerized using a radical initiator, and at the end of the polymerization, 0.07 parts by weight of calcium stearate and 0.7 parts by weight of HCAo were added per 100 parts by weight of the resulting copolymer. A copolymer was obtained by processing in a conventional manner.

The obtained copolymer was directly pelletized in the same manner as in Example 1 and evaluated.

The experimental results are shown in Table 1.

[Effects] The high nitrile resin composition of the present invention has improved adhesion to metals such as screws during molding without impairing transparency.

Therefore, if the resin composition of the present invention is used, it will have excellent transparency, and the adhered residue will not get mixed into the molded product due to burning and impair the properties such as the excellent gas barrier properties that the high nitrile resin has. Good molded products can be obtained.

In addition, since burnt material hardly stops adhering to dies, screws, etc., the molding machine does not need to be disassembled and cleaned as often, and productivity can be expected to improve.

Claims (1)

[Claims] 1. 0.01 to 1 part by weight of a fatty acid metal salt and 0.01 to 1 part by weight of a compound represented by general formula (1) are added to 100 parts by weight of a high nitrile resin. High nitrile resin composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼Formula (1) [However, X and Y are an alkyl group, a halogen group, a halogenated alkyl group, an OH group, an amino group, a nitro group,
ROH group, RNH group, RNO group, COOR group, OR group,
Or represents water, an RNO group, a COOR group, an OR group, or a hydrogen atom. Note that R is CnH2n+1 (n=1 to 2
0), an alkylene group of CnH2n, or an aryl group. 2. The high nitrile resin composition according to claim 1, wherein the fatty acid metal salt is calcium stearate or magnesium stearate. 3. The compound represented by the general formula (1) is 9,10-dihydro-9-phosphor-10-oxaphenanthrene-
The high nitrile resin composition according to claim 1, which is a 9-oxide. 4. The high nitrile resin composition according to claim 3, wherein the fatty acid metal salt is calcium stearate or magnesium stearate.