JPH0551508A - High-nitrile resin composition - Google Patents

Abstract

PURPOSE:To provide a high-nitrile resin composition which is prevented from generating acrylonitrile due to thermal decomposition during molding and has high transparency and a good color tone. CONSTITUTION:The title composition comprises 100 pts.wt. high-nitrile resin having an acrylonitrile content of 50-90wt.% and 0.05 to less than 5 pts.wt. one or more terpenes selected from among dlcamphor, citronellal, and geraniol.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high nitrile resin composition, and more specifically, it has an acrylonitrile content of 50 to 90% by weight, and suppresses the production of acrylonitrile due to thermal decomposition during resin molding. And a high nitrile resin composition having excellent transparency and good color tone.

[0002]

BACKGROUND OF THE INVENTION High nitrile resins have good chemical resistance and excellent gas barrier properties, and are therefore useful as container materials for foods, cosmetics, perfumes and the like. However, high nitrile resin has a high melt viscosity and is sensitive to shearing force, so if a high shear is applied during molding,
Acrylonitrile produced by the thermal decomposition of the resin remains in the molding material or molded product to cause a sanitary problem, and there is a drawback that the color tone of the resin becomes yellow due to the temperature rise of the resin.

JP-A-58-40340 and 60-21.
Each of the publications of No. 2448 proposes a resin composition in which the production of acrylonitrile is suppressed. These compositions are characterized by adding a mercapto compound and a terpene compound or a mercapto compound and an alcohol compound to an acrylonitrile-based thermoplastic resin. However, all of the above proposals are directed to resins having an acrylonitrile content of up to about 30% by weight, and the acrylonitrile content is 50% by weight or more, which is considered to be poor in thermal stability. Not applicable to nitrile resins.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is a high nitrile resin having an acrylonitrile content of 50% or more,
An object of the present invention is to provide a high nitrile resin in which generation of acrylonitrile due to thermal decomposition at the time of molding a resin is suppressed and which has good transparency and color tone.

[0005]

That is, the gist of the present invention is one kind selected from the group of d1-camphor, citronellal and geraniol with respect to 100 parts by weight of a high nitrile resin having an acrylonitrile content of 50 to 90% by weight. Alternatively, a high nitrile resin composition is characterized in that two or more kinds of terpene compounds are added in a range of 0.05 parts by weight or more and less than 5 parts by weight.

The present invention will be described in detail below. The high nitrile resin used in the present invention is a resin containing 50 to 90% by weight of a nitrile monomer unit based on the weight of the whole polymer. Here, the weight percentage of the nitrile monomer unit is
It is calculated as acrylonitrile. As the nitrile monomer, acrylonitrile, methacrylonitrile, glutaronitrile, methyleneglutaronitrile,
Examples include fumaronitrile and a mixture of these monomers.

The monomers copolymerized with the nitrile monomer are preferably aromatic monomers such as styrene and α-methylstyrene, and 2 to 6 carbon atoms such as propylene, butylene and isobutylene. And lower alpha olefins containing Also, acrylic acid and alkyl groups are 1 to
Corresponding acrylates containing 6 carbon atoms (eg methyl acrylate, ethyl acrylate,
Propyl acrylate, butyl acrylate, etc.), methacrylic acid and corresponding methacrylates in which the (cyclo) alkyl group contains from 1 to 6 carbon atoms (eg methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, etc.) are also suitable. Mentioned as a monomer. Further, vinyl ester such as vinyl acetate, alkyl vinyl ether having an alkyl group containing 1 to 4 carbon atoms, and ethyl vinyl ether are also preferable. Each of the above monomers can be used alone or as a mixture of two or more. The high nitrile resin used in the present invention may be rubber-reinforced with polybutadiene or the like.

The resin composition of the present invention is obtained by adding a specific terpene compound to the above high nitrile resin. The terpene compound used in the present invention is d1-camphor, citronellal or geraniol. These terpene compounds are added to the high nitrile resin to maintain the transparency of the high nitrile resin, suppress the generation of acrylonitrile due to thermal decomposition during molding of the resin, and exhibit the effect of improving the color tone.

The above terpene compounds may be used alone or
It is possible to use two or more kinds in combination, but the addition amount must be in the range of 0.05 parts by weight or more and less than 5 parts by weight with respect to 100 parts by weight of the high nitrile resin, and the preferable addition amount is 0. The range is from 1 part by weight to 2 parts by weight. If the addition amount of the terpene compound is less than the above range, the desired effect of the present invention cannot be obtained, and if it is more than the above range, not only the acrylonitrile production suppressing effect is not so remarkable, but also the transparency. In addition, the heat resistance is deteriorated, and an odor problem may occur.

The terpene compound may be added to the high nitrile resin by a conventional mixer such as a ribbon mixer,
Using a Henschel mixer, tumbler, etc., appropriately adopt a method of mixing a high nitrile resin and a predetermined amount of a terpene compound, or a method of adding a predetermined amount of a terpene compound to a high nitrile resin melt-mixed in an extruder. You can

Since the high nitrile resin composition of the present invention contains a specific terpene compound, the production of acrylonitrile is suppressed, and as a result, the residual amount of acrylonitrile in the molding material or molded article is 10 ppm or less. Will be reduced. The high nitrile resin composition of the present invention exhibits excellent chemical resistance and gas barrier properties due to the high acrylonitrile content, and is particularly suitable for packaging applications.

[0012]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the example below,
All "parts", "percentages", and "ppm" are based on weight. Moreover, the addition amount of the additive has shown the addition amount with respect to 100 weight part of high nitrile resin.

The measurement of physical properties and the like were carried out by the following methods. (1) Amount of residual acrylonitrile in resin (hereinafter referred to as “RAN
It is abbreviated as "amount"). A sample dissolved in DMF is measured with a gas chromatograph equipped with an FTD detector, and the content of p relative to the resin is p.
It is shown in pm. (2) Transparency of resin Haze was measured with a direct reading haze computer by Suga Test Instruments, and%
Expressed as (3) Color of resin Yellowness (Yell
ow Index: reflection method) was measured and shown as yellowness. (4) Fluidity (MFR) and heat distortion temperature It was measured by the JIS method.

Examples 1 to 6 Using 30 parts of styrene (St) as a comonomer, 70 parts of acrylonitrile (AN) was copolymerized by ordinary suspension polymerization to obtain a beaded high nitrile resin. Based on 100 parts of the above resin, 0.14 parts of butylated hydroxytoluene (BHT) as an antioxidant, 0.035 part of glycerin fatty acid ester, 0.015 part of polyoxyethylene sorbitan fatty acid ester and o / p-toluene sulfone. 0.15 parts of amide-formaldehyde resin was added to make a basic formulation. For the above basic formulation,
As shown in Table 1, a predetermined amount of the terpene compound specified in the present invention was added and mixed for 1 minute with a super mixer.
Pelletization was performed with a mmφ bus co-kneader. After drying the resulting pellets, using a 3OZ injection molding machine,
Molded product (2.6mm × 65mm)
A 75 mm flat plate and a 1/4 "bar) were obtained. The RAN amount, haze, yellowness, melt flow rate, and heat distortion temperature of the molded product were measured. The measurement results are shown in Table 1.

[0015]

[Table 1] ──────────────────────────────────── Example Additives RAN Haze Yellowness MFR Heat distortion temperature (part) (ppm) (g / 10min) (℃) ────────────────────────────────── ─── 1 dl camphor 0.3 8.9 2.6 108 5.1 93 2 dl camphor 0.6 8.2 2.6 106 5.8 93 3 citronellal 0.3 8.7 2.5 106 5.3 93 4 citronellal 0.6 8.0 2.5 103 6.0 93 5 geraniol 0.3 9.8 3.5 108 5.2 93 6 geraniol 0.6 9.1 3.8 105 6.1 93 ─────────────────────────────────────

Comparative Examples 1 to 16 Molded articles were obtained and their physical properties were measured in the same manner as in the above Examples except that the type and amount of the additives were changed. The measurement results are shown in Table 2.

[0017]

[Table 2] ──────────────────────────────────── Example Additives Additive RAN Haze Yellowness MFR Heat distortion temperature (part) (ppm) (g / 10min) (℃) ────────────────────────────────── ─── 1 − 0 16.3 3.5 125 4.1 94 2 dl camphor 0.04 16.3 2.6 125 4.1 94 3 dl camphor 6.0 8.0 4.3 145 12.0 82 4 citronellal 6.0 8.0 5.5 153 13.0 83 5 caffeine 0.5 20.5 3.6 106 4.5 93 6 caffeine 6.0 22.0 4.2 135 5.1 81 7 Nellore 1.0 15.7 18.1 120 5.2 92 8 α-Turbineol 1.0 14.5 19.7 106 5.3 91 9 Citronellol 1.0 15.3 17.5 116 5.5 91 10 α-Yonone 1.0 16.3 12.0 109 5.1 91 11 Myrcene 0.5 8.5 13.0 105 4.9 92 12 Citral 0.5 16.5 4.4 106 4.7 92 13 Citral 2.0 17.4 12.3 115 4.7 88 14 Vinyl stearate 0.5 15.7 80.0 117 5.1 92 15 Triaryl cyanurate 0.1. 5 18.0 4.3 124 5.1 92 16 Flaxseed oil 0.1 17.0 50.0 111 4.0 93 ──────────────────────────────────── ─

Examples 7 to 8 and Comparative Example 17 50 parts of acrylonitrile was used and 50 parts of styrene was used as a copolymerization monomer to carry out copolymerization by ordinary suspension polymerization to obtain a bead-like high nitrile resin. To 100 parts of the above resin, 0.14 part of BHT, 0.035 part of glycerin fatty acid ester, 0.015 part of polyoxyethylene sorbitan fatty acid ester and 0.15 part of o / p-toluenesulfonamide-formaldehyde resin were added. To give the basic formulation. As shown in Table 3, a predetermined amount of the terpene compound specified in the present invention was added to the above basic composition, mixed for 1 minute with a super mixer, and pelletized with a 46 mmφ bus cokneader. The pellets obtained were dried and then molded using a 3OZ injection molding machine under the conditions of 360 ° C. to obtain a molded product (2.6 mm × 65 mm × 75 mm
A flat plate and a 1/4 "bar) were obtained. The RAN amount, haze, and yellowness of the above molded product were measured. The measurement results are shown in Table 3 as Examples 7 to 8. Note that additives were not used. The physical properties of the molded product obtained without the measurement were measured in the same manner as above, and the results are shown in Table 4 as Comparative Example 17.

[0019]

[Table 3] ─────────────────────────────── Example Resin composition Additive amount RAN haze Yellowness AN / St ( (Part) (ppm) (%) ─────────────────────────────── 7 50/50 dl camphor 0.5 8.8 2.3 68 8 50/50 Citronellal 0.5 9.1 2.3 66 ───────────────────────────────

[0020]

[Table 4] ─────────────────────────────── Example Resin composition Additive amount RAN haze Yellowness AN / St ( (Part) (ppm) (%) ─────────────────────────────── 17 50/50 − 0 15.5 2.5 88 ── ─────────────────────────────

Comparative Examples 18 to 20 60 parts of styrene as a comonomer was used for 40 parts of acrylonitrile, and copolymerization was carried out by an ordinary suspension polymerization to obtain a nitrile resin having an acrylonitrile content of 40% by weight.
Based on 100 parts of the above resin, 0.14 parts of butylated hydroxytoluene (BHT) as an antioxidant, 0.035 part of glycerin fatty acid ester, 0.015 part of polyoxyethylene sorbitan fatty acid ester and o / p-toluene sulfone. Amide-formaldehyde resin 0.15
Parts to make a basic formulation. As shown in Table 5, a predetermined amount of the terpene compound specified in the present invention was added to the above-mentioned basic composition, a molded article was obtained in the same manner as in Examples, and the physical properties were measured. In addition, the physical properties of the molded product obtained without using the additives were measured in the same manner as above. The results obtained are shown in Table 5.

[0022]

[Table 5] ─────────────────────────────── Example Resin composition Additive amount RAN haze Yellowness AN / St ( (Part) (ppm) (%) ─────────────────────────────── 18 40/60 − 0 18 2.5 55 19 40 / 60 dl camphor 0.5 19 2.6 56 20 40/60 citronellal 0.5 18 2.6 54 ────────────────────────────────

[0023]

According to the present invention described above, by adding a specific amount of a specific terpene compound, the production of acrylonitrile due to thermal decomposition during molding of a resin is suppressed, and a high nitrile having good transparency and color tone is obtained. A resin composition is provided. Therefore, the industrial value of the present invention is great.

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[Procedure amendment]

[Submission date] April 15, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0005

[Correction method] Change

[Correction content]

[0005]

That is, the gist of the present invention is one kind selected from the group of d1-camphor, citronellal and geraniol with respect to 100 parts by weight of a high nitrile resin having an acrylonitrile content of 50 to 90% by weight. Alternatively, the high nitrile resin composition is characterized in that two or more kinds of terpene compounds are added in a range of 0.05 parts by weight or more and less than 5 parts by weight.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

[0017]

[Table 2] ──────────────────────────────────── Example Additives Additive RAN Haze Yellowness MFR Heat distortion temperature (part) (ppm) (g / 10min) (℃) ────────────────────────────────── ─── 1 − 0 16.3 3.5 125 4.1 94 2 dl camphor 0.04 16.3 2.6 125 4.1 94 3 dl camphor 6.0 8.0 4.3 145 12.0 82 4 citronellal 6.0 8.0 5.5 153 13.0 83 5 camphene 0.5 20.5 3.6 106 4.5 93 6 camphene 6.0 22.0 4.2 135 5.1 81 7 Nellore 1.0 15.7 18.1 120 5.2 92 8 α-Turbineol 1.0 14.5 19.7 106 5.3 91 9 Citronellol 1.0 15.3 17.5 116 5.5 91 10 α-Yonone 1.0 16.3 12.0 109 5.1 91 11 Milsen 0.5 8.5 13.0 105 4.9 92 12 Citral 0.5 16.5 4.4 106 4.7 92 13 Citral 2.0 17.4 12.3 115 4.7 88 14 Vinyl stearate 0.5 15.7 80.0 117 5.1 92 15 Triallyl cyanurate 0. 5 18.0 4.3 124 5.1 92 16 Flaxseed oil 0.1 17.0 50.0 111 4.0 93 ──────────────────────────────────── ─

Claims (1)

[Claims] 1. 0.05 part by weight of one or more terpene compounds selected from the group consisting of d1-camphor, citronellal and geraniol per 100 parts by weight of a high nitrile resin having an acrylonitrile content of 50 to 90% by weight. A high nitrile resin composition, characterized by being added in an amount of less than 5 parts by weight.