JPH0616931A - Solvent resistant vessel - Google Patents

Abstract

PURPOSE:To obtain a solvent resistant vessel containing a polyamide resin, a modified polyolefin, etc., and a modified olefin based elastomer in specific amounts and excellent in mechanical strength, oil resistance, impact resistance, etc. CONSTITUTION:The vessel contains (A) 50-90wt.% polyamide resin (preferably nylon 66, etc.), (B) 2-40wt.% modified polyolefin (preferably obtained by modifying a polyethylene having 5-20 melt index/10min with a carboxy or epoxycontaining monomer) or a polyolefin resin composition (obtained by diluting a modified polyolefin with an unmodified polyolefin) containing >=10% modified olefin based elastomer and (C) 5-30wt.% modified olefin based elastomer (obtained by modifying an olefinic elastomer with a monomer having carboxy or epoxy) or an olefinic elastomer composition (obtained by diluting a modified olefin based elastomer with an unmodified olefinic elastomer) containing >=10% modified olefinic elastomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solvent-resistant container containing a polyamide resin as a main component, and particularly to solvent resistance, oil resistance,
The present invention relates to a solvent resistant container made of a polyamide resin composition having excellent impact resistance and mechanical strength.

[0002]

BACKGROUND OF THE INVENTION Polyamide resins are excellent in mechanical strength, heat resistance, gas barrier properties and the like, and are therefore suitable for plastic containers replacing various metal containers and glass containers. In particular, it has attracted attention as an industrial container such as a solvent container and a tool box.

However, the polyamide resin has a problem that it is inferior in water resistance, moldability and impact resistance. In particular, since it has poor impact resistance, it has a problem that it does not have sufficient strength as an industrial container that is expected to be used under severe conditions.

The above-mentioned insufficient properties are generally possessed by polyolefins. However, since the polyolefin resin is inferior in solvent resistance and oil resistance, there is a problem that swelling or cracking is easily caused by oil components such as engine oil. Therefore, with a polyamide resin layer,
A modified polyolefin layer and a container having a multilayer structure composed of a polyolefin layer are used, but if the adhesion between the layers is not sufficient, mechanical strength and impact resistance tend to decrease,
In addition, solvent resistance, oil resistance, water resistance and the like are likely to decrease due to defects in the multilayer structure. Further, since the processing process becomes complicated, there is a problem that the manufacturing cost becomes high.

Therefore, although a container made of a polyamide resin single layer is desired, there is a problem that the compatibility between polyamide and polyolefin is not good. Therefore, for the purpose of improving the compatibility between the polyamide and the polyolefin, it is possible to add a modified polyolefin such as an unsaturated carboxylic acid or an anhydride thereof,
There is a problem in that it is difficult to bring all of the mechanical strength, impact resistance, solvent resistance and oil resistance required for a solvent resistant container to good levels simply by adding a modified polyolefin.

Therefore, an object of the present invention is to provide a solvent resistant container made of a polyamide resin composition which is excellent in solvent resistance, oil resistance, impact resistance and mechanical strength.

[0007]

As a result of earnest research in view of the above object, the present inventors have prepared a polyamide resin, a modified polyolefin by a modifying monomer having a carboxyl group or an epoxy group, and a modified olefin elastomer. The container obtained from the composition containing a predetermined amount,
The present invention has been accomplished by discovering that it has excellent solvent resistance, oil resistance, impact resistance, mechanical strength, etc., and is suitable as a solvent resistant container.

That is, the solvent resistant container of the present invention comprises: (a) 50 to 90% by weight of polyamide resin; (b) modified polyolefin; or 2 to 40% by weight of a polyolefin resin composition containing 10% by weight or more of the modified polyolefin. % And (c)
A modified olefin-based elastomer or a composition containing 5 to 30% by weight of an olefin-based elastomer composition containing 10% by weight or more of the modified olefin-based elastomer.

The present invention is described in detail below. The solvent resistant container of the present invention is basically (a) a polyamide resin, and (b)
It comprises a modified polyolefin and (c) a modified olefin elastomer. Each component will be described below.

(A) Polyamide Resin In the present invention, (a) the polyamide resin includes hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4- or 2,4,4, -trimethylhexamethylenediamine, Aliphatic, alicyclic or aromatic diamines such as 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane), m- or p-xylylenediamine, and adipine A polyamide produced from an aliphatic, alicyclic or aromatic dicarboxylic acid such as an acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid or isophthalic acid, 6
From polyamides prepared from aminocarboxylic acids such as aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, polyamides prepared from lactams such as ε-caprolactam, ω-dodecalactam, and components thereof And a mixture of these polyamides. Specific examples include nylon 6, nylon 66, nylon 610, nylon 9, nylon 6/66, nylon 66/610, nylon 6/11, nylon 6/12, nylon 12, nylon 46, and amorphous nylon. . Of these, nylon 6 and nylon 66 are preferable in terms of good rigidity and heat resistance.

The molecular weight of the above polyamide resin is not particularly limited, but those having a relative viscosity η _r (measured in JIS K6810, 98% sulfuric acid) of 0.5 or more are usually used, and those having a mechanical strength of 2.0 or more are particularly used. It is preferable because it is excellent.

(B) Modified Polyolefin (b) The modified polyolefin is a modified polyolefin with a monomer having a carboxyl group or an epoxy group.

In the modified polyolefin, the polyolefin to be modified is ethylene, propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, etc. Examples thereof include a copolymer with propylene or another α-olefin, or a copolymer of two or more kinds of these α-olefins. Among these, polyethylene such as low density polyethylene, linear low density polyethylene, medium density polyethylene and high density polyethylene and polypropylene are preferable. Polypropylene is not limited to a homopolymer, and a random or block copolymer with another α-olefin containing a propylene component in an amount of 50 mol% or more, preferably 80 mol% or more can also be used. As the comonomer copolymerized with propylene, there are ethylene and other α-olefins, and ethylene is particularly preferable.

Melt index of the polyethylene
(MI, 190 ° C., 2.16 kg load) is preferably 0.1 to 100 g / 10 min, and particularly preferably 5 to 20 g / 10 min.

The polypropylene melt flow rate (MFR, 230 ° C., 2.16 kg load) is preferably 0.1 to 100 g / 10 min, and particularly preferably 0.5 to 10 g / 10 min.

Examples of such a polyolefin-modifying monomer include a monomer containing a carboxyl group or an epoxy group.

The carboxylic group-containing monomer is preferably an unsaturated carboxylic acid or an anhydride thereof, for example, a monocarboxylic acid such as acrylic acid or methacrylic acid, maleic acid,
Dicarboxylic acids such as fumaric acid and itaconic acid, maleic anhydride, itaconic anhydride, endo-bicyclo- [2,2,1] -5
Examples thereof include dicarboxylic acid anhydrides such as -heptene-2,3-dicarboxylic acid anhydride (hymic anhydride), and dicarboxylic acid and its anhydride are particularly preferable.

Further, as the epoxy group-containing monomer,
For example, methacrylic acid glycidyl ester, acrylic acid glycidyl ester and the like can be mentioned.

Further, the following general formula (1):

[Chemical 1] (In the formula, R is H or an alkyl group having 1 to 6 carbon atoms,
Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms and having at least one glycidyloxy group, and n represents an integer of 1 to 4. A glycidyl compound having an acrylamide group and an epoxy group represented by the formula (4) can also be used as the modifying monomer.

Preferred glycidyl compounds include those represented by the following general formula (2).

[Chemical 2] (In the formula, R is H or an alkyl group having 1 to 6 carbon atoms.)

Such a glycidyl compound can be produced, for example, by the method disclosed in JP-A-60-130580.

The modified polyolefin with the modifying monomer may be a block copolymer, a graft copolymer, a random copolymer or an alternating copolymer.

It is preferable that the content of the modifying monomer in the modified polyolefin is in the range of 0.05 to 5% by weight, preferably 0.1 to 3% by weight. If the amount of modification by the modifying monomer is less than 0.05% by weight, the effect of improving the compatibility between the polyolefin and the polyamide resin will not be sufficient, and if it exceeds 5% by weight, the mechanical strength will decrease.

The modified polyolefin can be produced by either a solution method or a melt kneading method. In the case of the melt-kneading method, the polyolefin, the modifying monomer and the catalyst are put into an extruder, a biaxial kneader or the like, and heated to a temperature of 180 to 250 ° C. to be kneaded while melting. In the case of the solution method, the above-mentioned starting materials are dissolved in an organic solvent such as xylene and the stirring is carried out at a temperature of 90 to 140 ° C. In any case, a usual radical polymerization catalyst can be used as a catalyst, for example, benzoyl peroxide, lauroyl peroxide, ditert-butyl peroxide, acetyl peroxide, tert-butyl peroxybenzoic acid, dicumyl peroxide, Peroxybenzoic acid, peroxyacetic acid, tertiary butyl peroxypivalate, peroxides such as 2,5-dimethyl-2,5-ditertiary butyl peroxyhexyne and diazo compounds such as azobisisobutyronitrile Etc. are preferred. The amount of the catalyst added is about 1 to 100 parts by weight based on 100 parts by weight of the modifying monomer.

Regarding the melt viscosity of the modified polyolefin as described above, in the case of modified polypropylene, the melt flow rate (MFR, 230 ° C., 2.16 kg load) is preferably 0.1 to 500 g / 10 minutes, and in the case of modified polyethylene. , Melt index (MI, 190 ℃, 2.16kg load) 1-50g / 1
It is preferably 0 minutes.

In the present invention, a polyolefin resin composition obtained by diluting the above modified polyolefin with an unmodified polyolefin can also be used. As the unmodified polyolefin, the above-mentioned polyolefin to be modified can be used.

In the case of the polyolefin resin composition, the ratio of the modified polyolefin is 10% by weight or more based on 100% by weight of the modified polyolefin and the unmodified polyolefin. When the content of the modified polyolefin is less than 10% by weight, there is no sufficient effect for improving the compatibility between the polyolefin resin composition (modified polyolefin + unmodified polyolefin) and the polyamide resin.

However, the modified polyolefin + unmodified polyolefin is 100% by weight, and the content of the modifying monomer is preferably 0.01% by weight or more, and particularly preferably 0.05 to 5% by weight. When the content of the modifying monomer is less than 0.01% by weight, there is no sufficient effect for improving the compatibility between the polyolefin resin and the polyamide resin, which is not preferable.

(C) Modified Olefin-based Elastomer (c) The modified olefin-based elastomer is obtained by modifying the olefin-based elastomer with a monomer having a carboxyl group or an epoxy group.

In the modified olefin elastomer, the olefin elastomer to be modified is ethylene, propylene, butene-1, hexene-1,4-
Examples thereof include copolymer rubbers of two or more kinds of α-olefins such as methylpentene-1, and copolymer rubbers of α-olefins and other kinds of monomers. As the above-mentioned two or more copolymer rubbers of α-olefin, typically, ethylene-propylene copolymer rubber (EPR), ethylene-butene copolymer rubber (EBR), and ethylene-propylene- Diene copolymer rubber (EPDM) may be mentioned. As the diene in the ethylene-propylene-diene copolymer rubber (EPDM), a non-conjugated diene such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene or a conjugated diene such as butadiene or isoprene is used. be able to. Further, vinyl acetate, acrylic acid ester and the like can be used as the other monomer copolymerized with the α-olefin. A typical example of a copolymer of α-olefin and another monomer is ethylene-
Examples thereof include vinyl acetate copolymer (EVA).

Ethylene-propylene copolymer rubber (EPR)
Preferably has an ethylene content of 40 to 90 mol% and a propylene content of 10 to 60 mol%. A more preferable range is 50 to 90 mol% of ethylene and 10 to 10 of propylene.
It is 50 mol%.

The EPR melt index (190
C., 2.16 kg load) is preferably in the range of 0.5 to 15 g / 10 minutes, more preferably 3 to 9 g / 10 minutes.

The ethylene-butene copolymer rubber (EBR) is
The ethylene content is preferably 60 to 97 mol%, and the butene-1 content is preferably 3 to 40 mol%. A more preferred range is 80 to 95 mol% for ethylene and 5 to 20 mol% for butene-1.

Further, the EBR melt index (190
C., 2.16 kg load) is preferably in the range of 0.5 to 15 g / 10 minutes, more preferably 3 to 9 g / 10 minutes.

The ethylene-propylene-diene copolymer (EPDM) has an ethylene content of 40 to 89 mol%, a propylene content of 10 to 59 mol%, and a diene content of 1 to 10 mol%. % Is preferable.

Furthermore, the Mooney viscosity of EPDM ML _{1 + 8} (100
C.) is preferably in the range of 5 to 100, more preferably 10 to 50.

The ethylene-propylene-diene copolymer rubber (EPDM) and the ethylene-propylene copolymer rubber (EPR) basically consist of the above repeating units. Within the range that does not impair the characteristics, for example, butene-1 or 4-methylpentene-1
Other repeating units, such as repeating units derived from α-olefins such as, may be included up to a proportion of 10 mol% or less.

Further, in the present invention, a hydrogenated styrene-butadiene block copolymer (SEBS: styrene-ethylene / butylene-polymer) is used as the olefin elastomer.
Styrene block copolymer), hydrogenated styrene-isoprene block copolymer (SEPS: styrene-ethylene
An elastomer such as propylene-styrene block copolymer) can also be used.

The content of styrene in the above elastomer component is preferably 5 to 50% by weight, and its MFR (230 ° C., 2.16 kg) is preferably in the range of 0.1 to 100 g / 10 minutes. , More preferably 1 to 50 g / 10
Minutes.

As the monomer for modifying such an olefinic elastomer, the same one as the above-mentioned modified polyolefin can be used.

The content of the modifying monomer in the modified olefin elastomer is 0.05 to 5% by weight, preferably 0.1 to 5.
It is preferable that the content is within the range of 3% by weight. When the amount of modification by the modifying monomer is less than 0.05% by weight, the effect of improving the compatibility between the olefin elastomer and the polyamide resin is not sufficient, and when it exceeds 5% by weight, the mechanical strength decreases.

The modified olefin elastomer can be produced by either a solution method or a melt-kneading method, as in the case of the above modified polyolefin. In the case of the melt kneading method, the olefin elastomer, the modifying monomer and the catalyst are put into an extruder, a twin-screw kneader or the like, and heated to a temperature of 150 to 250 ° C. to be kneaded while melting. In the case of the solution method, the above starting materials are dissolved in an organic solvent such as xylene,
Stir at a temperature of ~ 140 ° C.

In the present invention, an olefinic elastomer composition obtained by diluting the above-mentioned modified olefinic elastomer with an unmodified olefinic elastomer can also be used. As the unmodified olefin-based elastomer, the above-described modification-target olefin-based elastomer can be used.

In the case of an olefin elastomer composition,
The ratio of the modified olefin elastomer is 10% by weight or more based on 100% by weight of the modified olefin elastomer and the unmodified olefin elastomer. When the content of the modified olefin-based elastomer is less than 10% by weight, there is no sufficient effect for improving the compatibility between the olefin-based elastomer and the polyamide resin.

However, modified olefin elastomer +
The unmodified olefinic elastomer is 100% by weight, and the content of the modifying monomer is 0.05% by weight or more, and especially 0.
It is preferably from 2 to 3% by weight. When the content of the modifying monomer is less than 0.05% by weight, there is no sufficient effect for improving the compatibility between the olefin elastomer and the polyamide resin, which is not preferable.

The mixing ratio of each component as described above is (a)
The polyamide resin is 50 to 90% by weight, preferably 55 to 85% by weight, and (b) the modified polyolefin (or the polyolefin resin composition containing the same) is 2 to 40% by weight, preferably 5 to 30% by weight. And (c) the modified olefin elastomer (or the olefin elastomer composition containing the same) is 5 to 30% by weight, preferably 10 to 30% by weight.

If the polyamide resin content is less than 50% by weight, the mechanical strength and heat resistance are insufficient, while if it exceeds 90% by weight, the impact resistance is lowered.

When the content of the modified polyolefin (or the polyolefin resin composition containing the same) is less than 2% by weight,
The water resistance is not sufficient, while if it exceeds 40% by weight, impact resistance and oil resistance are deteriorated.

The modified olefin elastomer (or the olefin elastomer composition containing the same) is 5
If less than wt%, the impact resistance is not sufficient, while 30 wt%
If it exceeds, heat resistance and mechanical strength will decrease.

For the purpose of modifying the composition used in the solvent resistant container of the present invention, other additives such as an inorganic filler, a heat stabilizer, an antioxidant, a light stabilizer and a refractory agent are added. A flame retardant, a plasticizer, an antistatic agent, a release agent, a nucleating agent, etc. can be added.

The above composition can be obtained by kneading in a molten state at 220 to 300 ° C. using an extruder such as a single screw extruder or a twin screw extruder.

The composition as described above can be made into a solvent resistant container by a usual molding method such as extrusion blow molding or injection molding.

In the case of extrusion blow molding, for example, a cylindrical ballison is extruded at a temperature of 220 to 280 ° C. from an extrusion blow molding die having an annular orifice connected to an extruder, and the parison is shaped into a cavity having a desired container shape. The container can be manufactured by installing the mold in a mold having the above and then blowing. The blow molded solvent resistant container obtained as described above is suitable for having a capacity of about 0.1 to 20 liters, and the wall thickness of the container is about 1 to 3 mm.

In the case of injection molding, for example, a container can be produced by injecting a molten resin composition at 220 to 300 ° C. into a mold having a desired cavity. Injection-molded containers obtained as described above are 2-40
It is suitable to have a capacity of about 1 liter, and the thickness of the container is about 1 to 3 mm.

As a solvent-resistant container, solvent resistance and oil resistance are generally important regardless of the wall thickness, volume, etc. of the container. The solvent-resistant container of the present invention satisfies the above conditions, although it is necessary that no swelling, cracking, or the like occurs when it is immersed for 300 to 3000 hours.

The extrusion blow-molded container and the injection-molded container as described above can be used as a can-shaped body, a box-shaped body or the like by cutting at a desired position. Also, other components (eg, cap, lid, handle, spout, etc.) are bonded to the containers of various shapes obtained in this way by heat fusion, ultrasonic fusion, application of adhesive, etc. Alternatively, it can be attached and used by fitting.

[0057]

The solvent-resistant container of the present invention comprises a polyamide resin,
Since it is obtained from a composition containing a modified polyolefin having a modifying monomer having a carboxyl group or an epoxy group and a modified olefin elastomer in a predetermined amount, solvent resistance, oil resistance, impact resistance and mechanical properties It has good mechanical strength and is suitable for industrial applications such as solvent containers and tool boxes.

Although the reason why such an effect is obtained is not necessarily clear, a machine having a polyamide resin can be prepared by blending a polyamide resin, a modified polyolefin and a modified olefin elastomer within the scope of the present invention. Strength, heat resistance, gas barrier properties, solvent resistance and oil resistance, water resistance of polyolefin, and impact resistance of olefin elastomer,
It is considered that each of them is well-balanced as a solvent resistant container.

[0059]

The present invention will be described in more detail by the following examples. The following resin components were used as raw materials. [1] Polyamide resin Ny6: [EMS, A28] [2] Modified polyolefin / maleic anhydride modified polypropylene CMPP: [Tonen Kagaku, C915X, maleic anhydride addition 0.2% by weight] [ 3] Modified olefin elastomer-maleic anhydride modified ethylene-propylene copolymer rubber CMEPR [Tonen Kagaku KK, HA75, 0.8% by weight of maleic anhydride added] [4] Polyolefin-propylene-ethylene block copolymer Combined BPP: [BJ-503 manufactured by Tonen Chemical Co., Ltd.]

Examples 1 to 4 and Comparative Examples 1 to 4 Nylon (Ny6), polypropylene (BPP), modified polypropylene (CMPP) and modified olefin elastomer (CMEPR) were dry-blended in the blending ratios shown in Table 1, The mixture was kneaded at 250 ° C. with a 40 mmφ twin-screw extruder to obtain pellets of the composition.

Using the obtained pellets, a test piece for a physical property test described later was prepared by injection molding, and the flexural modulus, Izod impact strength, and engine oil resistance were evaluated. The results are shown in Table 2.

Table 1 Composition (parts by weight) Example 1 Example 2 Example 3 Example 4 Ny6 60 60 60 80 CMPP 30 10 20 10 CMEPR 10 10 20 10 BPP-20 ---

Table 1 (continued) Composition (parts by weight) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Ny6 100-70 90 CMPP--30-CMEPR--10 BPP-100 ---

Table 2 Physical Properties Example 1 Example 2 Example 3 Example 4 Flexural modulus ⁽¹⁾ Drying conditions 16000 16000 13000 21000 Moisture absorbing conditions 7500 7500 6500 8000 Izod impact strength ⁽²⁾ 23 ° C. NB ^* NB ^* NB ^* NB ^* -30 ° C 10 8 NB ^* 13 Engine oil resistance ⁽³⁾ Presence or absence of swelling ○ ○ ○ ○ Presence of cracks ○ ○ ○ ○ Note) *: Not broken.

Table 2 (continued) Physical Properties Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Flexural Modulus ⁽¹⁾ Drying Conditions 25000 13000 21000 23000 Hygroscopic Conditions 8000 13000 15000 6500 Izod Impact Strength ⁽²⁾ 23 ° C 4 20 6 20 -30 ° C 3 8 5 6 Engine oil resistance ⁽³⁾ Presence or absence of swelling ○ × ○ ○ Presence of cracks ○ × ○ ○ Note) *: Not broken.

(1) Flexural modulus: at 23 ° C., ASTM D790
Measured under dry conditions and under hygroscopic conditions (when the test piece was immersed in warm water at 50 ° C to absorb water up to the equivalent of 50% RH saturated water absorption) (unit: kg / cm ² ). (2) Izod impact strength: ASTM at 23 ℃ and -30 ℃
Measured by D256 (unit is kgcm / cm). (3) Engine oil resistance: Dumbbell-shaped test pieces used in JIS K7113 were used, and after soaking in engine oil (120 ° C) for 300 hours without stressing the test pieces,
The presence or absence of swelling and cracks is visually confirmed, and as for swelling, those that are not swollen at all are evaluated as ○, those that are slightly swollen are evaluated as Δ, and those that are clearly swollen are evaluated as ×, and cracks Was evaluated as ◯ when no crack was observed at all and evaluated as x when cracking occurred.

As is clear from Table 2, Examples 1 to 4
The composition (1) had excellent impact resistance and excellent flexural modulus under dry and hygroscopic conditions, and neither swelling nor cracking was observed even when immersed in engine oil. On the other hand, the compositions of Comparative Examples were inferior in impact resistance, flexural modulus, or engine oil resistance.

[0068]

As described in detail above, the solvent resistant container of the present invention comprises a polyamide resin, a modified polyolefin containing a modifying monomer having a carboxyl group or an epoxy group, and a modified olefin elastomer in a predetermined amount. Since it is obtained from the composition containing it, it has good solvent resistance, oil resistance, impact resistance, mechanical strength and the like.

The solvent resistant container of the present invention can be a container manufactured by various molding methods such as an extrusion blow molding container and an injection molding container. Such a solvent resistant container of the present invention is suitable for industrial use such as a solvent container and various tool boxes.

Claims (1)

[Claims] 1. (a) 50 to 90% by weight of polyamide resin,
(b) a modified polyolefin, or 2 to 40% by weight of a polyolefin resin composition containing 10% by weight or more of the modified polyolefin, and (c) a modified olefin elastomer,
Or 10% by weight of the modified olefin elastomer
A solvent resistant container comprising a composition containing 5 to 30% by weight of the olefin elastomer composition contained above.