JPH08311301A - Abs resin composition for calendering - Google Patents

Abstract

PURPOSE: To obtain an ABS resin composition having excellent moldability in calendering and giving a film having excellent chemical resistance and light resistance. CONSTITUTION: This ABS resin composition for calendering has a melt flow rate of 5-30g/10min under 10kg load at 220 deg.C and contains 100 pts.wt. of an ABS resin and 0.5-5 pts.wt. of a polycaprolactone having a weight-average molecular weight of >=60,000. The above resin composition may further contain 5-50wt.% of a methacrylic resin having a melt flow rate of 5-15g/10min under 3.8kg load at 230 deg.C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an ABS for calendar molding.
A resin composition and an ABS resin film obtained by calendar molding.

[0002]

2. Description of the Related Art Styrene resins are widely used for general electric appliances such as household electric equipment parts, various automobile interior and exterior parts, office furniture parts and the like. Among styrene resins, ABS resin is a resin that has a good balance of chemical resistance and mechanical strength. In recent years, vinyl chloride resin has been restricted in Europe and other countries due to environmental problems, so it is also used as a substitute material. Is being started.

One of them is an export film produced by a calendering method, and currently ABS resin is mainly used. However, the ABS resin film is produced by the calendering method because of the roll releasability that it is difficult to peel from a high temperature roll when calendering with ABS resin, and the thermal deterioration property that discoloration occurs due to the heat of the high temperature roll and oxygen in the atmosphere. Was difficult. Therefore, conventionally, it has been a mainstream to manufacture a film by blending a release agent and a plasticizer. However, when a release agent or a plasticizer is used, the film surface tends to be rough. Regarding discoloration prevention as well, when various additives are added, the surface of the film is likely to become rough, as in the case of the release agent. Therefore, there is a demand for a method of improving moldability by using a polymer alloy or the resin itself, instead of adding a compounding agent or an additive.

In general households, alcohol-based liquids are sometimes used for cleaning purposes to wipe off stains. Therefore, A produced by calendar molding is used.
In order to use the BS resin film for protection of furniture doors, decorative films, etc., chemical resistance to alcohol is required. Generally, ABS resin has light resistance, chemical resistance,
In particular, it is weak against alcohol, and in applications such as protection of furniture doors and decorative films, the molding strain is doubled during calendar molding, pasting, and so on.
When a resin is used, there is a problem in that when an alcohol-based cleaning agent is used, cracks and cracks are considerably generated.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to heat deterioration resistance,
Excellent roll peelability and sufficient chemical resistance on a daily basis.
It is an object of the present invention to provide an ABS resin composition having excellent calendar formability, which enables a calendar film having light resistance.

[0006]

The present invention is as follows. 1. 100 parts by weight of ABS resin contains 0.5 parts by weight or more and 5 parts by weight or less of polycaprolactone having a weight average molecular weight of 60,000 or more, and a melt flow rate at a temperature of 220 ° C. and a load of 10 kg is 5 g / 10 minutes or more 30 g / 10 ABS-based resin composition for calendar molding having a content of not more than a minute. 2. Polycaprolactone having a weight average molecular weight of 60,000 or more and 0.5 parts by weight or more and 5 parts by weight or less, and a temperature of 230 ° C. and a load of 3.8 kg have a melt flow rate of 5 g / 10 min or more and 15 g / 10 min. Content of 5% or more and 50% or less by weight of methacrylic resin and a melt flow rate of 5 g at a temperature of 220 ° C. and a load of 10 kg.
/ 10 minutes or more and 30 g / 10 minutes or less ABS resin composition for calendar molding. 3. A calendar film produced by calendar molding using the ABS resin composition for calendar molding according to 1 or 2 above.

The present invention will now be described in detail below. The ABS resin as used in the present invention means a graft polymer obtained by graft-polymerizing a monomer made of a monomer containing butadiene with a monomer containing aromatic vinyl or vinyl cyanide, and an aromatic resin. It is a resin containing a copolymer produced from vinyl-vinyl cyanide-another copolymerizable monomer.

It is essential that the rubber used in the graft polymer contains butadiene, and other monomers such as aromatic vinyl, vinyl cyanide, acrylate, vinyl carboxylate and other monomers copolymerized with butadiene. Can also be copolymerized. The content of butadiene in the rubber is preferably 70% by weight or more, more preferably 80% by weight or more. Examples thereof include polyenes, styrene-butadiene copolymers, diene-based copolymers such as acryllotryl-butadiene copolymers, hydrogenated diene-based polymers, and the like. Among these, polybutadiene is preferable.

The graft polymer can be obtained by graft-polymerizing aromatic vinyl or vinyl cyanide on the above rubber. At that time, if necessary, an acrylic ester, a vinyl carboxylate compound, a maleimide vinyl compound or the like may be added. It is also possible to use other polymerizable monomers together in the graft polymerization. The rubber in the graft polymer is 5% by weight to 7%.
It is preferably adjusted to be 0% by weight, more preferably 10% to 60% by weight. The aromatic vinyl compound in the monomer to be graft-polymerized is preferably adjusted to 30% by weight to 80% by weight, and 40% by weight to 70% by weight.
It is more desirable to adjust so that The vinyl cyanide compound in the monomers to be graft-polymerized is 5
It is preferably adjusted to be 80% by weight to 80% by weight, more preferably 10% to 70% by weight.

Copolymers prepared from other aromatic vinyl-vinyl cyanide-copolymerizable monomers copolymerize aromatic vinyl and vinyl cyanide during the graft polymerization of the graft polymer or separately. In this case, other copolymerizable monomers such as acrylic acid ester, vinyl carboxylate compound, maleimide vinyl compound and the like can be used together, if necessary. Aromatic vinyl compound in the copolymer is 30% by weight to 80% by weight
Is preferably adjusted to 40% by weight to 70% by weight, and more preferably adjusted to 40% by weight to 70% by weight. The vinyl cyanide compound in the copolymer is preferably adjusted to 5 to 80% by weight, more preferably 10 to 70% by weight.

Aromatic vinyls used in rubbers, graft polymers, and copolymers prepared from other aromatic vinyl-vinyl cyanide-copolymerizable monomers include styrene and α-methylstyrene. , Α-chlorostyrene, bromostyrene, p-methylstyrene, etc.
One kind or a mixture of two or more kinds is used. Of these, styrene and α-methylstyrene are preferable. The same aromatic vinyl can be obtained even if different aromatic vinyls are used in the copolymer produced from rubber, graft polymer and other monomer capable of copolymerizing aromatic vinyl-vinyl cyanide-copolymer. You may use.

Similarly, vinyl cyanide used in rubbers, graft polymers and copolymers prepared from other aromatic vinyl-vinyl cyanide-copolymerizable monomers includes acrylonitrile and methacrylonitrile. Examples thereof include nitrile and the like, and one kind or a mixture of two or more kinds is used. After all, different vinyl cyanides or the same vinyl cyanide may be used.

Further, graft polymers and aromatic vinyl-
Examples of the maleimide vinyl compound used in the copolymer produced from vinyl cyanide-copolymerizable other monomer include an N-alkyl-substituted maleimide having an alkyl group having 1 to 4 carbon atoms and N-phenylmaleimide. , N-phenylmaleimide, N-cyclohexylmaleimide and the like. Among these, N-phenylmaleimide is preferable. The N-substituted maleimide also includes, for example, one obtained by copolymerizing maleic anhydride and then imidizing it with aniline or the like.

Further, graft polymers and aromatic vinyl-
Examples of the acrylic acid ester used in the copolymer produced from vinyl cyanide-copolymerizable monomer include alkyl methacrylate such as methyl methacrylate having 1 to 12 carbon atoms, methyl acrylate and the like. Examples of the alkyl group include alkyl acrylates having 1 to 12 carbon atoms. Further, as the vinyl carboxylate compound used in the graft polymer and the copolymer produced from other aromatic vinyl-vinyl cyanide-copolymerizable monomers, acrylic acid, maleic anhydride, methacrylic acid, etc. Is mentioned. The rubber can be produced by any of solution polymerization, bulk polymerization and emulsion polymerization. When the graft polymerization in the latter step is carried out in an emulsion state, it is produced by solution or bulk polymerization and then emulsified if necessary, or it is originally produced by emulsion polymerization.

The graft polymer can be obtained by graft-polymerizing the above-obtained rubber with aromatic vinyl, vinyl cyanide or another copolymerizable monomer. Graft polymerization can be carried out by any of solution polymerization, bulk polymerization and emulsion polymerization, but emulsion polymerization is preferred. A non-graft copolymer may be formed as a by-product in the course of this graft polymerization, and this is included in the copolymer prepared from other aromatic vinyl-vinyl cyanide-copolymerizable monomers. When a copolymer produced from another aromatic vinyl-vinyl cyanide-copolymerizable monomer is produced in a separate step, any of solution polymerization, bulk polymerization and emulsion polymerization can be carried out.

The ABS resin of the present invention contains the above-mentioned graft polymer and a copolymer produced from an aromatic vinyl-vinyl cyanide-copolymerizable other monomer, but if necessary, other In addition to the thermoplastic resin, lubricants, antistatic agents, antioxidants, flame retardants, ultraviolet absorbers, colorants,
It is also possible to incorporate foaming agents, fibrous and granular inorganic fillers, or also other compounding agents and additives commonly used in thermoplastic resin compositions. Examples of other thermoplastic resins include polycarbonate, thermoplastic polyurethane, and polyester.

For mixing the ABS resin of the present invention with each component, various mixing devices generally used for thermoplastic resins such as an extruder with a vent, a plastomill, a kneader, a Banbury mixer, and a Brabender can be used. Of these, a vented extruder is preferred. In the first invention, polycaprolactone having a weight average molecular weight of 60,000 or more is 0.5
It is necessary that the content is not less than 5 parts by weight and not more than 5 parts by weight,
It is preferable that the weight average molecular weight of 70,000 or more is contained in an amount of 1 part by weight or more and 4 parts by weight or less.

In the present invention, polycaprolactone is
Highly crystalline, biodegradable, low melting high molecular weight thermoplastics used as chemical resistance improvers. If the weight average molecular weight is less than 60,000, the effect as a chemical resistance improver is small, so it is necessary to increase the compounding amount.
Moldability deteriorates. Further, the material cost is high and it is not economically preferable. In terms of production, only those having a molecular weight of up to about 80,000 are produced. The compounding amount of polycaprolactone is 0.
If the amount is less than 5 parts by weight, the compounding amount is small and the effect of chemical resistance is difficult to appear. If it is more than 5 parts by weight, the moldability will deteriorate. In addition, the material cost is high, which is not economically preferable.

In the first invention, it is necessary that the melt flow rate is adjusted to 5 g / 10 minutes or more and 30 g / 10 minutes or less, preferably 7 g / 10 minutes or more and 20 g / 10 minutes or less by a method according to JIS standard K7210. is there. When the melt flow rate is less than 5 g / 10 minutes, the temperature of the calender roll cannot be molded unless the temperature is 200 ° C. or higher, so the temperature is high and cooling takes time, resulting in poor productivity. When the melt flow rate is more than 30 g / 10 minutes, the elongational viscosity is low, and necking is apt to occur at the time of take-up, which makes it difficult to take it out. The melt flow rate is controlled by the amount of rubber in the ABS resin composition, the particle size of graft-polymerized particles, the molecular weight of a copolymer obtained by polymerizing a monomer containing aromatic vinyl-vinyl cyanide, and the like. Graft polymer particle size is 0.05 μm
The molecular weight of the copolymer is preferably adjusted to 30,000 or more and 200,000 or less.

The second invention is that the melt flow rate is AS.
5% by weight or more and 5% by weight or more and 15 g / 10 minutes or less, preferably 8 g / 10 minutes or more and 13 g / 10 minutes or less of a methacrylic resin by a method according to TM standard D1238 (I).
Contains 0 wt% or less. If the melt flow rate of the methacrylic resin is less than 5 g / 10 minutes, the roll temperature must be raised considerably, cooling will take time, and the productivity will drop. If it is more than 15 g / 10 minutes, the elongational viscosity will be low and necking will occur during take-up, making it difficult to wind. Further, the blending amount is adjusted to 5% by weight or more and 50% by weight or less, preferably 20% by weight or more and 45% by weight or less. If the blending amount is less than 5% by weight, the effects of heat deterioration resistance and light resistance cannot be seen,
If it is more than 50% by weight, the moldability becomes poor.

The melt flow rate of the ABS resin composition containing the methacrylic resin of the second invention is 5 g / 10 minutes or more and 30 g / 1 according to the method according to JIS K7210.
It is adjusted to 0 minutes or less, preferably 7 g / 10 minutes or more and 20 g / 10 minutes or less. If the melt flow rate is less than 5 g / 10 min, the film cannot be formed into a film unless the temperature of the calender roll is increased, resulting in poor cooling efficiency. When the melt flow rate is higher than 30 g / 10 minutes, the elongational viscosity at the time of melting becomes too low, and necking is likely to occur at the time of drawing the film, which makes it difficult to manufacture the film.

The third invention is the AB of the first or second invention.
It is a calendar film produced using an S-based resin composition, and the thickness of this film is preferably 0.1 mm or more and 10 mm or less, more preferably 0.2 mm or more and 0.4 mm or less. This calendar film can be manufactured by a general calendar forming method. First, raw materials, stabilizers, pigments, etc. are premixed by a premixer or the like, supplied to a kneading device, and charged and rolled into continuously combined rolls. It is a method of cooling this, cutting both ends to make the width uniform, and automatically winding. If this film is used, it can be used as a decorative film for protecting houses such as furniture doors having excellent light resistance and chemical resistance. Since the conventional ABS resin has poor light resistance and chemical resistance, when an alcohol-based cleaning agent is used for cleaning, cracks and cracks easily occur.

Examples of the present invention will be described below.

[0024]

【Example】

[0025]

Examples 1 to 3 Polycaprolactone having a weight average molecular weight of 70,000 shown in Table 1 was added to acrylonitrile /
It is blended in an ABS resin having a styrene / butadiene composition ratio (weight ratio), uniformly dispersed by a Henschel mixer, and then extruded into pellets by a single-screw extruder. The composition extruded into pellets has a melt flow rate of JI
8g / 10 minutes according to S standard K7210,
It was almost the same as the melt flow rate of the ABS resin before compounding. The above composition was subjected to a temperature of 195 using a calendar molding machine (NS-200 (J) W manufactured by Nishimura Koki Co., Ltd.).
Calendar molding was performed at 0 ° C. to prepare a calendar film having a thickness of 0.2 mm.

As a result, the peelability from the calendar roll was extremely good, and the surface was clean without rough skin. In addition, the melting time of the composition was shortened and the productivity could be improved. The calendered film was thermoformed at a temperature of 130 ° C. and attached on a plywood, and its chemical resistance was confirmed. Regarding the chemical resistance, methanol was applied to the surface of the film, and it was observed whether cracks or cracks occurred. As a result, no cracks or cracks were found. The results are shown in Table 1. The peelability was evaluated as ◯ when the film was peeled from the calendar roll, and as × when the film was not peeled from the calendar roll. The film appearance was evaluated as ◯ when it was clean without wrinkles and without rough skin, and as x when there were wrinkles and rough skin. The chemical resistance was evaluated as ◯ when cracks and cracks were not visually observed, and as x when cracks and cracks were visually recognized.

[0027]

[Comparative Examples 1 and 2] Examples 1 to 2 except that polycaprolactone having a weight average molecular weight of 70,000 and an ABS resin having an acrylonitrile / styrene / butadiene composition ratio (weight ratio) shown in Table 1 were used in the amounts shown in Table 1. A calendar film was molded in the same manner as in 3. The results are shown in Table 1.

[0028]

Examples 4 to 6 ABS resin having an acrylonitrile / styrene / butadiene composition ratio (weight ratio) shown in Table 2, polycaprolactone having a weight average molecular weight of 70,000 and methacrylic resin (Delpet 560F manufactured by Asahi Kasei Kogyo Co., Ltd., 670
N, 80N) were mixed in the amounts shown in Table 2, uniformly dispersed by a Henschel mixer, and then extruded into pellets by a single-screw extruder. The extruded ABS resin composition in pellet form was subjected to a roll temperature of 195 using an 8-inch test roll.
Calendering was carried out at a temperature of ℃ and a film thickness of 0.2 mm. As a result, the peelability from the calendar roll was extremely good. Further, to 100 parts by weight of the ABS resin composition, 10 parts by weight of a titanium oxide pigment (AS resin: titanium oxide = 2: 8) dispersed in the AS resin was added to form a white film, and a Suga test was conducted. The change in color tone was measured by changing the roll residence time with an SM color computer SM-3 type manufactured by Kiki Co., Ltd. As shown in Table 2, the change due to heat was small. A white press-molded product (thickness: about 0.2 mm) was used as a blank product in the measurement. Light resistance is sunshine
The measurement was performed using a super long life weather meter (WEL-SUN-DCH type manufactured by Suga Test Instruments Co., Ltd.) at an atmospheric temperature of 63 ° C. without rainfall. The blank product used had an exposure time of 0 hours. In addition, all samples used had a roll residence time of 5 minutes. The results are shown in Tables 2 and 3.
Regarding chemical resistance, no cracks or cracks were found. As a result, as shown in Tables 2 and 3, the values were equivalent to those of the conventional vinyl chloride resin film and were good.

[0029]

Comparative Examples 3 to 6 Example 4 except that polycaprolactone having a weight average molecular weight of 70,000, ABS resin and methacrylic resin having the composition ratio (weight ratio) of acrylonitrile / styrene / butadiene shown in Table 2 were used in the amounts shown in Table 2. A calendar film was formed in the same manner as in the above-mentioned procedure. The results are shown in Tables 2 and 3.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

The ABS resin composition of the present invention has excellent calender moldability, and the obtained film has excellent heat deterioration resistance, roll peelability, chemical resistance and light resistance, and is suitable for furniture and the like. It is very useful as a film for surface protection or decoration.

Claims (3)

[Claims] 1. An ABS resin containing 100 parts by weight of polycaprolactone having a weight average molecular weight of 60,000 or more in an amount of 0.5 to 5 parts by weight, a temperature of 220 ° C. and a load of 10 kg.
Melt flow rate of 5g / 10 minutes or more 30g / 10
ABS-based resin composition for calendar molding having a content of not more than a minute. 2. A polycaprolactone having a weight average molecular weight of 60,000 or more and 0.5 parts by weight or more and 5 parts by weight or less, and a melt flow rate of 5 g / 10 at a temperature of 230 ° C. and a load of 3.8 kg are added to 100 parts by weight of an ABS resin. ABS for calendar molding containing 5 wt% to 50 wt% of a methacrylic resin of 5 min to 15 g / 10 min and a melt flow rate of 5 g / 10 min to 30 g / 10 min at a temperature of 220 ° C. and a load of 10 kg. -Based resin composition. 3. The calendar forming A according to claim 1 or 2.
A calendar film produced by calendar molding using a BS-based resin composition.