JPH083455A - Synthetic resin composition - Google Patents

Abstract

PURPOSE:To obtain a synthetic resin compsn. which is excellent in heat resistance, cold resistance, flame retardance, moldability, mold release characteristics, impact resistance, and slidability and does not undergo the change with time due to bleed out of a silicone oil. CONSTITUTION:This synthetic resin compsn. is prepd. by compounding 100 pts.wt. synthetic resin with 0.1-50 pts.wt. silicone oil and 0.1-20 pts.wt. polylactone-modified polysiloxane.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a synthetic resin composition, and in particular, it has excellent heat resistance, cold resistance, flame retardancy, releasability, impact resistance, slidability, etc. The present invention relates to a synthetic resin composition that gives a resin molded product that does not change its properties with time.

[0002]

2. Description of the Related Art Synthetic resin compositions are widely used in various fields as various molding materials such as electric / electronic device parts, machine parts, automobile parts, daily necessities and food packaging. Although various characteristics are required for this synthetic resin composition depending on its application, heat resistance, cold resistance, flame retardancy, moldability, mold releasability, impact resistance, slidability, etc. are particularly required. It has been attempted to add dimethyl silicone oil to these products, and some effects have been achieved.

[0003]

However, since this dimethyl silicone oil has poor compatibility with synthetic resins, it is difficult to make it stably exist in synthetic resins, and this bleeds gradually over time. In many cases, the characteristics are deteriorated because it is out. Therefore, there is also 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 and an epoxy group, but in this case, the synthetic resin and this reactive group are The bleed-out phenomenon can be prevented in the case of a combination in which the two react with each other, but the results are similar to those of the dimethyl silicone oil in the other combinations.

For this reason, there has been proposed a method in which a polylactone-silicone copolymer which is solid at room temperature is used as the silicone which does not cause the bleed-out phenomenon (Japanese Patent Laid-Open Nos. 61-37843 and 61-37843). 63-187772, JP-A-2-272021, JP-A-4-100845), but these are intended to improve the properties of the synthetic resin only with an expensive lactone-silicone copolymer. From
There is a drawback that the application is limited because the synthetic resin using this is expensive.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a synthetic resin composition which solves the above disadvantages and drawbacks. It is 0.1 to 50 parts by weight of silicone oil and polylactone modified per 100 parts by weight of synthetic resin. Polysiloxane
It is characterized in that 0.1 to 20 parts by weight is added.

[0006] That is, the inventors of the present invention, heat resistance, cold resistance,
As a result of various studies to develop a synthetic resin composition that has excellent flame retardancy, moldability, mold release property, impact resistance, slidability, etc. and does not change over time due to bleeding out of silicone oil, In order to impart these physical properties to the synthetic resin, a silicone oil was added according to a known method, and a polylactone-modified polysiloxane was further added to the silicone oil to prevent the silicone oil from aging due to bleed-out. It was found that the bleed-out of silicone oil is prevented, and thus it is possible to prevent the aging of this thing,
The present invention has been completed by conducting research on the types and addition amounts of these silicone oils and polylactone-modified polysiloxanes. This will be described in more detail below.

[0007]

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

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, such as polyester resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride / vinyl acetate copolymer resin, polyvinyl acetal resin. , Polyvinyl alcohol resin, vinylidene chloride resin, polyethylene resin, polypropylene resin, polystyrene resin, acrylic resin, polyurethane resin, polyamide resin, polyacetal resin, ABS resin, thermoplastic resin such as AS resin,
Examples include thermosetting resins such as phenol 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 in order to make it excellent in flame retardancy, moldability, releasability, impact resistance, and slidability. This silicone oil can be arbitrarily selected from known ones. It is possible to use dimethyl silicone oil as the most common one, but some of the methyl groups are hydrogen atoms, phenyl groups, alkyl groups having 2 or more carbon atoms, hydroxyl groups, alkenyl groups, alkyl halides. 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. May be

Since this silicone oil is added to a synthetic resin, its viscosity at 25 ° C. is 5 to 5.
It should be 100,000,000 cS, preferably 50 to 100,000 cS. If this amount is less than 0.1 parts by weight relative to 100 parts by weight of the synthetic resin, the improvement of the physical properties will be insufficient and the addition of 50 parts by weight or more will be insufficient. If the amount is too large, the strength of the synthetic resin is lowered, so that it is required to be in the range of 0.1 to 50 parts by weight, and this is preferably 0.5 to 30 parts by weight.

The polylactone-modified polysiloxane added to this synthetic resin is a polylactone-bonded polylactone which is a ring-opening polymer of a lactone compound having a 5-membered ring or more 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, reduces the effect of preventing bleeding out of silicone oil, so it is recommended that the melting point be 40 ° C or higher. General formula (1)

[Chemical 4] [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 consisting of an unsubstituted or substituted phenyl group and an alkylene group having 2 or 3 carbon atoms] Identical or different groups,
R ² is a divalent organic group, R ³ is a hydrogen atom or 1 to 1 carbon atoms.
10 alkyl group, acyl group, A and B are alkyl groups having 1 to 4 carbon atoms or formula

Embedded image (R ² and R ³ are the same as above), which are 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

[Chemical 6] The following are preferred.] Are preferred.

Regarding 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 ,

[Chemical 7] The group represented by is exemplified, and 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 And R ³ is —H, —CH ₃ , — (CH ₂ ) ₃ C
H ₃ ,

[Chemical 9] What is shown by is illustrated.

When a in the general 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 when it exceeds 1,000, it is difficult to synthesize, and therefore a is an integer of 3 to 1,000. However, b is an integer of 0 to 50 because synthesis becomes difficult when it exceeds 50,
When c is less than 5, the melting point is less than 40 ° C. and the effect of preventing bleeding out of silicone oil is reduced, and when it exceeds 500, synthesis becomes difficult, so an integer of 5 to 500 is used.

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

[Chemical 10] (Here, A and B are alkyl groups having 1 to 4 carbon atoms or -R ² H
Then, R ¹ , R ² , a, b, and c are the same as above), and ε-caprolactone is subjected to ring-opening polymerization using a catalyst in the absence of a solvent or in a solvent diluted to the active hydrogen group-containing polysiloxane. Good.

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

According to this, the 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 one in which the terminal OH group is acylated by a known method or alkylated. it can. If the amount of this compound added to the synthetic resin is less than 0.1 parts by weight relative to 100 parts by weight of the synthetic resin, the bleed-out prevention effect of silicone oil will be insufficient, and if it exceeds 20 parts by weight, further improvement in performance cannot be expected. , 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight.

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

[0018]

[Examples] Next, synthesis examples of the polylactone-modified polysiloxane used in the present invention, and examples and comparative examples will be given. In the examples, parts are parts by weight, and viscosities are measured values at 25 ° C. The Izod impact strength and the coefficient of dynamic friction in the examples show the test results according to the following. (Izod impact strength) In accordance with ASTM D256,
Test using the Izod impact tester (manufactured by Toyo Seiki Co., Ltd.) at a test piece size of 6.3 x 12.7 x 3.2 mm and a temperature of 23 ° C. (Friction test) According to JIS K7204, test piece size 50 ×
80 x 1.2 mm flat plate cut into mating material S45C
(Approx. 0.8 μmRa), load 15.3 kgf, peripheral speed 50 cm / sec, measurement time 100 minutes.

(Polycaprolactone-modified polysiloxane synthesis example-1)

[Chemical 11] Silicone compound represented by (OH number 22KOHmg / g) 51
Weigh 0 g (0.1 mol) and 684 g (6.0 mol) of ε-caprolactone, add 0.24 g of tetrabutyl titanate as a catalyst to this, and then add 130 g of nitrogen gas.
The reaction was allowed to stir at ~ 140 ° C for 10 hours with a melting point of 54
° C below formula

[Chemical 12] Polycaprolactone-modified polysiloxane 1
1,170 g was obtained.

(Polycaprolactone-modified polysiloxane synthesis example-2)

[Chemical 13] Silicone compound represented by (OH number 94 KOHmg / g) 29
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 to this, and then nitrogen gas was passed in
When reacted at 30 to 140 ° C for 10 hours with stirring, the melting point was
58 ° C below formula

Embedded image Polycaprolactone-modified polysiloxane 2
1,388 g was obtained.

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

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

[0023]

[Table 1]

[Table 2]

Examples 4 to 5 Polyethylene terephthalate resin TR-4550BHK
Silicone oil KF-96H with a viscosity of 10,000 cS as shown in Table 3 in 100 parts of [Teijin Co., Ltd. product name]
(Previously mentioned) 5 parts and 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. , Using this injection molding machine 63mm × 12.7mm × 3.2mm
A bar was prepared to prepare a test piece, and an Izod impact test and a friction test were carried out on the test piece immediately after the test piece and the test piece after standing at 40 ° C. for 7 days, as shown in Table 4 below. The result was obtained.

Comparative Examples 3 to 4 For comparison, as shown in Table 3, a polyethylene terephthalate resin containing 40 parts of glass fiber and 3 parts of talc without adding silicone oil and polylactone-modified polysiloxane (Comparative Example 3). , And 100 parts of polyethylene terephthalate resin, 5 parts of silicone oil with a viscosity of 10,000 cS KF-96H (described above), 40 parts of glass fiber, and 3 parts of talc were added, but a polycaprolactone-modified polysiloxane was not added ( When the same test as in Example 3 was performed on Comparative Example 4), the results shown in Table 4 below were obtained regarding the Izod impact strength and the dynamic friction coefficient.

[0026]

[Table 3]

[Table 4]

[0027]

The synthetic resin composition of the present invention is a synthetic resin 100
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, which has heat resistance, cold resistance, flame retardancy and moldability. It has excellent releasability, impact resistance, and slidability, and is advantageous in that it does not change with time due to bleed-out of silicone oil.

Claims (3)

[Claims] 1. Silicone oil in 100 parts by weight of synthetic resin
0.1 to 50 parts by weight and polylactone-modified polysiloxane 0.1
A synthetic resin composition characterized by being added in an amount of up to 20 parts by weight. 2. A polylactone-modified polysiloxane is represented by the general formula: [Wherein R ¹ is the same as selected from an alkyl group having 1 to 30 carbon atoms, an unsubstituted or substituted phenyl group, and an unsubstituted or substituted phenyl group and a phenylalkylene group consisting of an alkylene group having 2 or 3 carbon atoms] Or a heterogeneous group, R
² is a divalent organic group, R ³ is a hydrogen atom or has 1 to 10 carbon atoms.
Is an alkyl group, an acyl group, A and B are alkyl groups having 1 to 4 carbon atoms, or (Wherein R ² and R ³ are the same as described above), which are the same or different groups, a is an integer of 3 to 1,000, and b is 0.
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 And 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.