JP2915793B2 - Synthetic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic resin composition, particularly excellent in heat resistance, cold resistance, flame retardancy, mold release, impact resistance, slidability and the like. The present invention relates to a synthetic resin composition that gives a resin molded product having no change in characteristics over time.

[0002]

2. Description of the Related Art Synthetic resin compositions are widely used in various fields as molding materials for electric / electronic equipment parts, mechanical parts, automobile parts, daily necessities, food packaging and the like. Various properties are required for this synthetic resin composition depending on its use, and heat resistance, cold resistance, flame retardancy, moldability, mold release, impact resistance, slidability, etc. are particularly required. For those that can be used, attempts have been made to add dimethyl silicone oil, and some effects have been achieved.

[0003]

However, since the dimethyl silicone oil has poor compatibility with the synthetic resin, it is difficult to stably exist the dimethyl silicone oil in the synthetic resin. In many cases, the characteristics are degraded due to the output. For this reason, there is a method of replacing this dimethyl silicone oil with a reactive silicone oil having a reactive group such as an amino group, a carboxy group, or an epoxy group. Bleed-out phenomenon can be prevented when the combinations are reactive with each other, but the other combinations produce the same result as dimethyl silicone oil.

For this reason, a method using a polylactone-silicone copolymer which is solid at room temperature as a silicone which does not cause a bleed-out phenomenon has been proposed (JP-A-61-37843, JP-A-61-37843). 63-187772, JP-A-2-272021 and JP-A-4-100845), but these are intended to improve the properties of synthetic resins using only expensive lactone-silicone copolymers. From
There is a drawback that the synthetic resin using this is expensive and its use is limited.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a synthetic resin composition which solves such disadvantages and drawbacks, comprising 0.1 to 50 parts by weight of silicone oil and 100 parts by weight of a synthetic resin and 100 parts by weight of a synthetic resin. Polysiloxane
It is characterized by adding 0.1 to 20 parts by weight.

That is, the present inventors have developed a heat resistance, a cold resistance,
As a result of various studies to develop a synthetic resin composition that has excellent flame retardancy, moldability, mold release properties, impact resistance, slidability, etc. and does not change over time due to bleed-out of silicone oil. A silicone oil was added according to a known method to impart these properties to the synthetic resin, and a polylactone-modified polysiloxane was further added to the silicone oil to prevent the silicone oil from changing over time due to bleed-out. It has been found that bleed-out of silicone oil is prevented, and therefore, it can be prevented from changing over time,
The present invention was completed by conducting research on the types and amounts of these silicone oils and polylactone-modified polysiloxanes. This is described in more detail below.

[0007]

The present invention relates to a synthetic resin composition,
This is characterized by adding 0.1 to 50 parts by weight of silicone oil and 0.1 to 20 parts by weight of polylactone-modified polysiloxane to 100 parts by weight of the synthetic resin as described above. Has the advantage that it has excellent heat resistance, cold resistance, flame retardancy, moldability, mold release, impact resistance, and slidability, and does not change over time due to bleed-out of silicone oil. Can be

[0008] The present invention relates to a synthetic resin composition, which is obtained by adding silicone oil and polylactone-modified polysiloxane to a synthetic resin. This synthetic resin is not particularly limited, and may be a known synthetic resin. Examples thereof include polyester resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, and polyvinyl acetal resin. , Thermoplastic resins such as polyvinyl alcohol resin, vinylidene chloride resin, polyethylene resin, polypropylene resin, polystyrene resin, acrylic resin, polyurethane resin, polyamide resin, polyacetal resin, ABS resin, AS resin,
Examples include thermosetting resins such as phenolic resins, urea resins, melamine resins, xylene resins, diallyl phthalate resins, unsaturated polyester resins, epoxy resins, and furan resins.

This synthetic resin has heat resistance, cold resistance,
Silicone oil is added to make it excellent in flame retardancy, moldability, mold release, impact resistance, and slidability, and this silicone oil can be arbitrarily selected from known ones. Dimethylsilicone oil is most commonly used for this purpose, and its methyl group is partially replaced with a hydrogen atom, phenyl group, alkyl group having 2 or more carbon atoms, hydroxyl group, alkenyl group, alkyl halide. Modified silicone oil substituted with a group, phenylalkyl group, amino group-containing group, epoxy group-containing group, carboxyl group-containing group, (meth) acryl group-containing group, mercapto group-containing group, carbinol group-containing group, polyether group, etc. It may be.

This silicone oil has a viscosity at 25 ° C. of 5 to 5 because it is added to a synthetic resin.
The amount should be 100,000,000 cS, preferably 50 to 100,000 cS.If the amount added is less than 0.1 part by weight with respect to 100 parts by weight of the synthetic resin, the improvement of the physical properties becomes insufficient because the amount is too small. When the amount is increased, the strength of the synthetic resin is reduced. Therefore, it is necessary to set the amount in the range of 0.1 to 50 parts by weight, but it is preferably 0.5 to 30 parts by weight.

The polylactone-modified polysiloxane added to the synthetic resin is a polylactone-bonded polylactone, which is a ring-opening polymer of a lactone compound having a 5- or more-membered ring such as ε-caprolactone, δ-valerolactone, and γ-butyrolactone. Siloxane, which has a melting point of less than 40 ° C., especially at room temperature or lower, the effect of preventing bleed-out of silicone oil is reduced, so it is preferable that the melting point be 40 ° C. or higher. General formula (1)

Embedded image [Wherein R ¹ is selected from an alkyl group having 1 to 30 carbon atoms, an unsubstituted or substituted phenyl group, and a phenylalkylene group composed of an unsubstituted or substituted phenyl group and an alkylene group having 2 or 3 carbon atoms] Same or different groups,
R ² is a divalent organic group, R ³ is a hydrogen atom or a carbon atom
10 alkyl groups, acyl groups, A and B are an alkyl group having 1 to 4 carbon atoms or a formula

Embedded image (R ² and R ³ are the same as described above), the same or different groups, a is an integer of 3 to 1,000, b is an integer of 0 to 50, c is an integer of 5 to 500, and b is When 0, at least one of A and B is a formula

Embedded image It is preferably represented by the following.

For each group in the compound represented by the general formula (1), R ¹ is -CH ₃ , -CH ₂ CH ₃ ,-
(CH ₂ ) ₃ CH ₃ ,-(CH ₂ ) ₉ CH ₃ ,-(CH ₂ ) ₂₉ CH ₃ ,

Embedded image Wherein R ² is -CH ₂ CH ₂ CH ₂ O-,
-CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ O-, -CH ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ ) ₂ O-, -C
H ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ ) ₁₀ O-, -CH ₂ S-, -CH ₂ CH ₂ CH ₂ S-,

Embedded image Wherein R ³ is -H, -CH ₃ ,-(CH ₂ ) ₃ C
H ₃ ,

Embedded image Are exemplified.

If a in formula (1) is less than 3, the effect of preventing bleed-out of the silicone oil in the synthetic resin of the present invention is small, and if it exceeds 1,000, the synthesis becomes difficult. And b is an integer of 0 to 50 since synthesis becomes difficult when b exceeds 50,
If c is less than 5, the melting point is less than 40 ° C., and the effect of preventing bleed-out of the silicone oil is reduced. If c exceeds 500, the synthesis becomes difficult, so that c is an integer of 5 to 500.

Although the method for synthesizing the polycaprolactone-modified polysiloxane represented by the general formula (1) is not particularly limited, it is well known that ε-caprolactone is ring-opened to an active hydrogen group-containing polysiloxane. It is preferable to adopt a method of polymerizing. Therefore, this is represented by the general formula (2)

Embedded image (Where A and B represent an alkyl group having 1 to 4 carbon atoms or -R ² H
Wherein R ¹ , R ² , a, b, and c are the same as those described above) and ring-opening polymerization of ε-caprolactone in a solvent-free or solvent-diluted catalyst with the active hydrogen group-containing polysiloxane represented by Good.

The catalyst may be a known one used for ring-opening polymerization of lactones, and thus includes an organic tin compound such as dibutyltin dioctate, dibutyltin dilaurate, or an organic tin compound such as tetraisopropyl titanate or tetrabutyl titanate. The titanium compound may be used, and the amount of the catalyst may be 5 to 5,000 ppm, preferably 20 to 500 ppm, based on the reaction system. This reaction proceeds even without solvent, but when the raw material active hydrogen group-containing polysiloxane or the target product has a high viscosity, it can be diluted with a solvent having no active hydrogen group such as toluene, xylene, diethylene glycol dimethyl ether. Good. This reaction may be carried out at 100 to 180 ° C., preferably 120 to 150 ° C., whereby the reaction can be completed in 3 to 10 hours.

According to this, a polylactone-modified polysiloxane represented by the general formula (1) can be obtained.
This can be used as one component of the synthetic resin composition of the present invention, but it is also possible to use a compound obtained by acylating or alkylating the terminal OH group by a known method. it can. If the amount added to the synthetic resin is less than 0.1 part by weight with respect to 100 parts by weight of the synthetic resin, the effect of preventing bleed-out of the silicone oil becomes insufficient. , 0.1 to 20 parts by weight, and preferably 0.5 to 10 parts by weight.

The synthetic resin composition of the present invention can be obtained by mixing a predetermined amount of the silicone oil and the polylactone-modified polysiloxane with the above-mentioned synthetic resin by dry blending, extrusion mixing, melt mixing, or the like. The synthetic resin composition obtained in this manner can be formed into a predetermined molded product by injection molding, extrusion molding, vacuum molding, or the like. If necessary, the composition may be reinforced with glass fiber, carbon, alumina, talc, or the like. Additives, lubricants such as higher fatty acids, higher fatty acid amides, paraffin wax, carnauba wax, polyethylene wax, plasticizers, antistatic agents, UV absorbers, flame retardants, antioxidants, stabilizers, colorants, etc. Optional.

[0018]

EXAMPLES Next, synthetic examples, examples and comparative examples of the polylactone-modified polysiloxane used in the present invention will be described. In the examples, parts are parts by weight and viscosity is a value measured at 25 ° C. The Izod impact strength and kinetic friction coefficient in the examples are the results of the following test. (Izod impact strength) According to ASTM D256,
The test is performed at 6.3 × 12.7 × 3.2 mm at a temperature of 23 ° C. using an Izod impact tester (manufactured by Toyo Seiki Co., Ltd.). (Friction test) Specimen size 50 × according to JIS K7204
80x1.2mm cut into flat plate, mating material S45C
(Approximately 0.8 μm Ra), load 15.3 kgf, peripheral speed 50 cm / sec, measurement time 100 minutes.

(Synthesis example of polycaprolactone-modified polysiloxane-1) The average formula was placed in a 2 liter flask.

Embedded image A silicone compound represented by the formula (OH value 22 KOHmg / g) 51
0 g (0.1 mol) and 684 g (6.0 mol) of ε-caprolactone were weighed, and 0.24 g of tetrabutyl titanate as a catalyst was added thereto.
When the reaction was carried out with stirring at 140 ° C for 10 hours, the melting point was 54
The following formula of ° C

Embedded image Polycaprolactone-modified polysiloxane 1 represented by
1,170 g were obtained.

(Synthesis Example 2 of Polycaprolactone-Modified Polysiloxane) The average formula was placed in a 2 liter flask.

Embedded image 29 (OH value 94 KOH mg / g)
8 g (0.1 mol) and 1,140 g (10.0 mol) of ε-caprolactone were weighed, and 0.36 g of dibutyltin dilaurate as a catalyst was added thereto.
The reaction was carried out with stirring at 30-140 ° C for 10 hours.
The following formula at 58 ° C

Embedded image Polycaprolactone-modified polysiloxane 2 represented by
1,388 g were obtained.

Examples 1 to 3 100 parts of a polypropylene resin, as shown in Table 1, a silicone oil having a viscosity of 10,000 cS or 1,000 cS.
96H or KF-96 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and the polycaprolactone-modified polysiloxane 1 or 2 obtained in Synthesis Examples 1 and 2 were added in the amounts shown in Table 1, and 170 ° C.
Was melt-kneaded under the conditions described above to prepare a synthetic resin composition, which was molded into a 100 mm x 250 mm x 1 mm plate using an injection molding machine to prepare a test piece. Then, the test piece immediately after molding and the test piece left for 7 days at 40 ° C. were placed on a polypropylene plate, a load of 200 gf was applied thereto, and the test piece was pulled at a pulling speed of 5 mm / min. When the coefficient of electrostatic friction was measured, the results as shown in Table 2 below were obtained for the appearance and the coefficient of electrostatic friction.

Comparative Examples 1-2 For comparison, a polypropylene resin containing no silicone oil and no polylactone-modified polysiloxane (Comparative Example 1), and a silicone oil having a viscosity of 10,000 cS / KF-96H (100 parts) were added to 100 parts of the polypropylene resin. The same test as in Example 1 was conducted on a composition (Comparative Example 2) to which 2 parts of the above) were added, but no polycaprolactone-modified polysiloxane was added. The appearance and the coefficient of static friction are shown in Table 2 below. The results were as expected.

[0023]

[Table 1]

[Table 2]

Examples 4 and 5 Polyethylene terephthalate resin TR-4550BHK
[Trade name of Teijin Limited] 100 parts of silicone oil KF-96H having a viscosity of 10,000 cS as shown in Table 3.
5 parts, 1 part each of the polycaprolactone-modified polysiloxane obtained in Synthesis Examples 1 and 2, 40 parts of glass fiber, and 3 parts of talc were added and melt-kneaded at 250 ° C. to prepare a resin composition. 63mm x 12.7mm x 3.2mm using an injection molding machine
A bar was prepared to prepare a test piece, and the Izod impact test and the friction test were performed on the test piece immediately after being obtained and the test piece left at 40 ° C. for 7 days. As shown in Table 4 below, Was obtained.

Comparative Examples 3 and 4 For comparison, as shown in Table 3, polyethylene terephthalate resin containing no silicone oil and no polylactone-modified polysiloxane but 40 parts of glass fiber and 3 parts of talc (Comparative Example 3) And 100 parts of polyethylene terephthalate resin, 5 parts of KF-96H silicone oil having a viscosity of 10,000 cS (described above), 40 parts of glass fiber, and 3 parts of talc, but not a polycaprolactone-modified polysiloxane. The same test as in Example 3 was performed on Comparative Example 4), and the results shown in Table 4 below were obtained for the Izod impact strength and the dynamic friction coefficient.

[0026]

[Table 3]

[Table 4]

[0027]

As described above, the synthetic resin composition of the present invention comprises 100 synthetic resins.
It is characterized by adding 0.1 to 50 parts by weight of silicone oil and 0.1 to 20 parts by weight of polylactone-modified polysiloxane to parts by weight, including heat resistance, cold resistance, flame retardancy, and moldability. It has the advantage that it has excellent release properties, impact resistance, and slidability, and does not change with time due to bleed-out of silicone oil.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08L 1/00-101/14

Claims (3)

(57) [Claims] 1. 100 parts by weight of synthetic resin and silicone oil
0.1 to 50 parts by weight and polylactone-modified polysiloxane 0.1
A synthetic resin composition characterized by adding up to 20 parts by weight. 2. The polylactone-modified polysiloxane has a general formula: [Wherein R ¹ is the same selected from an alkyl group having 1 to 30 carbon atoms, an unsubstituted or substituted phenyl group, and a phenylalkylene group composed of an unsubstituted or substituted phenyl group and an alkylene group having 2 or 3 carbon atoms] Or a different group, R
² is a divalent organic group, R ³ is a hydrogen atom or a C 1-10
And A and B are an alkyl group having 1 to 4 carbon atoms or a group represented by the formula: (Where R ² and R ³ are the same as above), the same or different groups, a is an integer of 3 to 1,000, b is 0 to
An integer of 50, c is an integer of 5 to 500, and when b is 0, at least one of A and B is The synthetic resin composition according to claim 1, having a melting point of 40 ° C or higher. 3. The synthetic resin composition according to claim 1, wherein the silicone oil is dimethyl silicone oil.