JPH0987532A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition which can give a molding having good blocking resistance and slipperiness without detriment to transparency when processed into films or sheet, while it retains excellent properties of a thermoplastic resin. SOLUTION: This thermoplastic resin composition comprises 100 pts.wt. thermoplastic resin and 0.1-10 pts.wt. spherical silicone gel particles having a mean particle diameter of 0.1-5μm and surface-treated with at least one member selected from the group consisting of organosiloxanediols of formula I (wherein R is methyl, trimethylsiloxy, vinyl or 3,3,3-trifluoropropyl) and organosiloxanediols of formula II (wherein R is as defined above; and (a) is 0, 1, 2 or 3).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition from which a molded article having excellent slipperiness and blocking resistance can be obtained.

[0002]

2. Description of the Related Art Polystyrene, polymethylmethacrylate, polypropylene, polyethylene, polyvinyl chloride,
Polyacetal, polyurethane, polyester, ABS,
Since thermoplastic resins such as AS have excellent moldability, processability, transparency, and easy coloring, and are inexpensive, they are used in large quantities as general-purpose resins and processed into various films, sheets, and molded products.

However, when processed into a sheet or film,
In particular, soft resins such as polyethylene, polyvinyl chloride, polypropylene, etc. have poor slidability and lubricity, so they are easy to block, and when the rolled product is unwound, it makes a strange noise, or when the sheets stick together. Easy to cause. Further, in the case of a hard resin such as polystyrene or polyacetal, the releasability of the molded product from the mold is poor, and improvement is required. Furthermore, since these resin molded products also have poor slidability, they not only hinder the improvement of productivity, but also the touch of the molded products is not good.

Therefore, in order to improve the sliding characteristics, it is usually practiced to add silicone oil, which is a lubricant excellent in chemical and physical stability, to these thermoplastic resins. However, since most of the oil near the surface layer of the molded product exudes and is consumed in a short time, it shows good slidability at the initial stage, but it is difficult to maintain good slidability for a long period of time. . Also, due to the silicone oil that exudes, there is stickiness on the surface of the molded product,
There is also the problem of reducing the product value.

As a method for solving these problems, a method of kneading a spherical silicone powder (for example, JP-A-1-168408, 1-204950 and JP-B-7-39214).
Or a method of kneading silicone rubber and polytetrafluoroethylene powder (JP-A-4-234450), a method of kneading silicone oil and polyvinylidene fluoride powder (JP-A-4-264152), and addition of spherical silica fine particles UV curable resins (Japanese Patent Application Laid-Open No. 7-102186) have been proposed, but the powder content of these powders is relatively high at 2 wt% or more, which is unsuitable for films and resin molded products requiring transparency. It is also economically disadvantageous. Further, the solid lubricant has a drawback that the slidability is gradually deteriorated due to abrasion powder caused by abrasion.

A method of kneading a silicone-grafted acrylic resin obtained by graft-copolymerizing an acrylic resin with a silicone macromonomer into a thermoplastic resin to obtain a slippery film or molded article (Japanese Patent Laid-Open No. 1-214475, Kaihei
4-173869 and Japanese Patent Laid-Open No. 6-100746) have also been proposed. However, since this silicone-grafted acrylic resin is so well compatible with the vinyl-based resin that it is well dispersed in the base material resin, the improvement of the slipperiness is insufficient with a small amount of the compound. In addition, since the silicone-grafted acrylic resin itself is an irregularly shaped powder, it may have the drawback of increasing the friction on the surface of the molded product.

In order to enhance the effect of improving the blocking resistance and slipperiness of the spherical silicone powder or silica powder, a technique of surface-treating these powders with a silane coupling agent is also known. Also in this case, the effect cannot be obtained unless a large amount of powder is added as in the above case.

[0008]

Therefore, the object of the present invention is to maintain good properties of a thermoplastic resin while maintaining transparency when processed into a film or sheet, while having good blocking resistance and slippage. It is intended to provide a thermoplastic resin composition capable of obtaining a molded article having properties.

[0009]

Means for Solving the Problems The present inventors have found that a spherical silicone gel having a special surface treatment is added in a small amount,
The inventors have found that blocking resistance and slipperiness are improved without impairing the transparency of the molded product, and the present invention has been completed.

That is, the present invention comprises (A) 100 parts by weight of a thermoplastic resin and (B) the formula (1):

[0011]

Embedded image (In the formula, R represents a methyl group, a trimethylsiloxy group, a vinyl group or a 3,3,3-trifluoropropyl group.)
And an organosiloxane diol represented by the formula (2):

[0012]

Embedded image (In the formula, R is as described above, and a is 0, 1, 2, or 3.) Average particle surface-treated with at least one selected from the group consisting of organosiloxane diols represented by A thermoplastic resin composition comprising 0.1 to 10 parts by weight of spherical silicone gel particles having a diameter of 0.1 to 5 μm.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION

(A) Thermoplastic resin As the thermoplastic resin, for example, polyethylene, polypropylene, polystyrene, polymethylmethacrylate,
AS resin, ABS resin, polyvinyl chloride, polyacetal,
Polyurethane, polyester, etc. are available and are not particularly limited. (B) Surface-treated spherical silicone gel particles The spherical silicone gel particles of the component (B) are surface-treated with the aforementioned organosiloxane diol so that silanol groups present on the surface are blocked.

The spherical silicone gel particles are composed of a monoorganosiloxane unit represented by the formula: R ¹ SiO _3/2 (wherein R ¹ is a monovalent organic group) as a main component and have a three-dimensional network formed by siloxane bonds. It is a spherical particle of a so-called polyorganosilsesquioxane having a structure, and the organic group bonded to a silicon atom (for example, R ¹ described above) includes, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. , Isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, alkyl group such as decyl group, cycloalkyl group such as cyclohexyl group, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group Group, alkenyl group such as hexenyl group, phenyl group, tolyl group, xylyl group, aryl group such as naphthyl group, benzyl group, phenyl group Niruechiru aralkyl group such as a group,
Further, some or all of the hydrogen atoms of these groups are fluorine,
Substituted with a halogen atom such as chlorine or bromine or a cyano group, for example, a chloromethyl group, a chloropropyl group, a bromoethyl group, a trifluoropropyl group or the like, usually having 1 to 10 carbon atoms, particularly an aliphatic unsaturated bond. Examples thereof include unsubstituted or substituted monovalent hydrocarbon groups having 1 to 6 carbon atoms. Among these, a lower alkyl group such as a methyl group is preferable from the viewpoints of availability of raw materials, ease of industrial production, and stability of silicone gel particles.
It may partially contain a vinyl group, a phenyl group, a 3,3,3-trifluoropropyl group or the like. Further, unless the effects of the present invention are impaired, spherical modified silicone gel particles containing a substituent having another functional group such as an amino group or a (meth) acryl group as an organic group bonded to a silicon atom are used. You can also

The spherical silicone gel particles are polyorganosilsesquioxane particles having a monoorganosiloxane unit as a basic constitutional unit as described above.
This contains a triorganosiloxy unit (R ¹ ₃ SiO _1/2 unit), a diorganosiloxane unit (R ¹ ₂ SiO _2/2 unit), a SiO _4/2 unit, etc. as a part of the constitutional unit. May be present (wherein R ¹ is as described above).

Such spherical silicone gel particles can be obtained by a known method, for example, by the following formula (3): R ¹ SiX ₃ (3) (wherein R ¹ has the same meaning as above. X is chlorine or bromine. And the like, which is a halogen atom or an alkoxy group having 1 to 4 carbon atoms) and which hydrolyzes an organosilane compound having a hydrolyzable group or atom in the presence of an acid or an alkali catalyst. can do. At this time, along with organosilane of Formula (1) in some cases, the _{^{formula: R 1 3 SiX, R 1}} 2 Si
One or more organosilanes having a hydrolyzable group or atom represented by X ₂ and SiX ₄ (wherein R ¹ and X are as described above) may be cohydrolyzed.

Usually, even if the spherical silicone gel particles obtained by the above-mentioned synthesis method are used as they are in the composition of the present invention in such a small amount that the transparency is not impaired, the slipperiness of the surface of the molded article obtained is obtained. , Blocking resistance is not improved.
It is considered that there is a considerable amount of silanol groups on the surface of the spherical silicone gel particles, which adversely affects the slipperiness and blocking resistance of the surface of the molded product.

It is considered that what is used as the component (B) in the present invention is surface-treated with the above-mentioned organosiloxane diol and the silanol groups present on the surface are blocked. Specifically, when the surface is treated with the organosiloxane diol represented by the formula (1), the surface is treated with the siloxane residue represented by the formula (4) below or the organosiloxane diol represented by the formula (2). When treated, it is presumed that it is blocked by the siloxane residue represented by the formula (5).

[0019]

Embedded image (R and a are the same as above) By this surface treatment, the silanol groups were inactivated, and the slipperiness and blocking resistance of the obtained molded product were greatly improved.

The above formula representing the organosiloxane diol
In (1) and (2), R is each independently a methyl group, a trimethylsiloxy group, a vinyl group, or 3, 3, 3
-Trifluoropropyl group, a is 0, 1, 2 or 3, and R is preferably a methyl group or a trimethylsiloxy group from the viewpoint of ease of compound synthesis, stability, blocking resistance and the like. And a is preferably 0 or 1.

Examples of such an organosiloxane diol include 1,1,1,3,7,7,7-heptamethyl-5- (trimethylsiloxy) tetrasiloxane-
3,5-diol, 1, 1, 1, 3, 5, 7, 7, 7-
Octamethyltetrasiloxane-3,5-diol,
3,5-bis (trimethylsiloxy) -1, 1, 1,
7,7,7-Hexamethyltetrasiloxane-3,5-
Diol, 1,1,1,1,7,7,7-hexamethyl-3,
5-divinyltetrasiloxane-3,5-diol,
1,1,1,1,7,7,7-hexamethyl-3,5-bis (trifluoropropyl) tetrasiloxane-3,5-
Diol, 1,3,3,5,5,5-hexamethyltrisiloxane-1,1-diol, 1-vinyl-3,3,3
5,5,5-pentamethyltrisiloxane-1,1-diol, 1- (trifluoropropyl) -3,3,5,5
5,5-pentamethyltrisiloxane-1,1-diol, 1,1,1,1,5,5,5-hexamethyltrisiloxane-3,3-diol 1,1,1,1,5,5,7,7 ,
7-octamethyltetrasiloxane-3,3-diol, 1,3,5,5,5-pentamethyl-3- (trimethylsiloxy) -trisiloxane-1,1-diol,
1,5,5,5-tetramethyl-3,3-bis (trimethylsiloxy) trisiloxane-1,1-diol,
Examples include 1,1,1,1,7,7,7-hexamethyl-5,5-bis (trimethylsiloxy) tetrasiloxane-3,3-diol.

The above-mentioned organosiloxane diol used as the surface treating agent can be produced by a known method.

In the case of a compound of formula (1), ie an organosiloxane diol each having one silanol group on the adjacent silicon atom, for example 1, 1, 1, 3,
5,7,7,7-octamethyl-3,5-dihydrotetrasiloxane and 3,5-bis (trimethylsiloxy)-
It can be obtained by a method of hydrolyzing 1,1,1,1,7,7,7-hexamethyl-3,5-dihydrotetrasiloxane with a Pd / C catalyst.

On the other hand, the compound of formula (2), that is, the organosiloxane diol having two silanol groups on the same silicon atom can be obtained by a known method as shown below.

[0025]

[Chemical 6] Also,

[0026]

[Chemical 7] Is based on the Kaeppler method [K. Kaeppler et al., J. Organomet. Che.
m., 402 (1991) 155].

The surface treatment can be easily performed by, for example, mixing and contacting untreated spherical silicone gel particles with the organosiloxane diol in a reaction vessel, and then performing heat treatment. When the above-mentioned organosiloxane diol is mixed and contacted, the organosiloxane diol may be mixed as it is, or water and spherical silicone gel particles may be mixed in advance and then the organosiloxane diol may be mixed and contacted. Can be used. In this case, the organosiloxane diol represented by the formula (1) and the organosiloxane diol represented by the formula (2) may be used alone or in combination of two or more, and the amount thereof is spherical. It is determined from the specific surface area of the silicone gel particles and the molecular occupied area of the organosiloxane diol represented by the formula (1) or (2), and is usually 0.05 to 10% by weight, preferably 0.1 to 5% by weight of the spherical silicone gel particles. Is.

The surface-treated spherical silicone gel particles have an average particle size of 0.1 to 5 μm, particularly 0.1 to 3 μm, from the viewpoint that the slipperiness of the surface of the obtained molded product is good.
Are preferred. It is presumed that if the average particle size is less than 0.1 μm, it becomes difficult for the particles to protrude from the surface, but the desired improvement in blocking resistance and slipperiness cannot be obtained, and if it exceeds 5 μm, the surface of the molded product The state becomes poor, and the transparency is significantly impaired when it is formed into a film.

The spherical silicone gel is, before or after the above surface treatment, increased in particle size by using a crusher such as a jet mill, a hammer mill or a ball mill so that the average particle size falls within the range of 0.1 to 5 μm. It is obtained as a spherical product by disintegrating.

The surface-treated spherical silicone gel particles
The amount of the component is 100 parts by weight of the thermosetting resin (A).
0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight
It is. If the compounding amount is less than 0.1 parts by weight, slip characteristics will be obtained.
If the amount exceeds 10 parts by weight, the sliding characteristics will remain within the head.
The dynamic friction system does not go down, which is economically disadvantageous. Preparation of composition Spherical silicone gel particles surface-treated with thermoplastic resin (A)
The present invention is prepared by blending the child (B) and heating and melting and kneading the mixture.
The composition of 1 is obtained as a kneaded product.

A product having excellent blocking resistance can be obtained by forming the kneaded product into a film or a sheet with a film forming machine or a sheet forming machine, and a container for medical products, a container for cosmetics, a container for foods can be obtained with various forming machines. , Or other various containers, electrical components, mechanical components, household items (eg cups,
It can be molded into dishes, agricultural and marine products, building materials, miscellaneous goods, toys (for example, plastic models), and the like.

For the purpose of further improving the slidability, the spherical silicone gel particles of the present invention are preliminarily treated with silicone oil,
A liquid lubricant such as a fluorinated oil can be impregnated. In addition, solid lubricants such as polytetrafluoroethylene, polyvinylidene fluoride, and graphite can be added to the composition of the present invention as long as the properties of the obtained molded product are not deteriorated. Further, as various auxiliary materials, a light stabilizer, an antioxidant, a filler, a colorant, a processability improving agent, an antistatic agent, an ultraviolet absorber, a pigment and the like can be added if necessary.

In the composition of the present invention, the respective components are uniformly dispersed at a predetermined ratio by a compounding machine such as a Henschel mixer, a ribbon blender, a high speed mixer, and further, a single-screw extruder, a twin-screw extruder, a Banbury mixer, pressurization. Kneader,
It can be obtained by uniformly kneading and dispersing using a kneader such as a kneader. The kneaded product thus obtained can be molded into a desired form using a mold by a conventional extrusion molding machine, injection molding machine, calender molding machine or the like. A T-die / sheet feeder, a roll sheet feeder or the like may be used to form a film or sheet, but the molding method is not particularly limited.

[0034]

EXAMPLES In the following description, parts means parts by weight. (1) Synthesis of spherical silicone gel particles Synthesis example 1 <Spherical silicone gel particles-I> 3,660 g of water having a pH of 6.8 and ammonia water (concentration 28
%) 90 g was added and stirred. The liquid mixture obtained was stirred at a speed of 200 rpm with a stirring blade under low speed stirring, and the liquid temperature was kept at 5 to 10 ° C.
While maintaining the above, 750 g of methyltrimethoxysilane was added dropwise over 3 hours. Further, after stirring for 4 hours while maintaining the liquid temperature at 5 to 10 ° C, the liquid temperature was heated to 40 to 50 ° C and stirred at that temperature for 1 hour. As a result, a silicone gel slurry was obtained. The silicone gel slurry thus obtained was filtered under pressure to form a cake having a water content of about 30%, and then dried in a drier at 105 ° C. The obtained dried product was crushed with a jet mill. When the obtained fine particles were observed with an electron microscope, they were spherical particles having a particle size of 1.6 to 2.0 μm, which are considered to have a large amount of active silanol groups on the surface. The particles thus obtained are called spherical silicone gel particles-I. Synthesis Example 2 <Spherical Silicone Gel Particles-II> 100 g of spherical silicone gel particles obtained in Synthesis Example 1-I and ion-exchanged water 1.
0 g was mixed with a mixer and heat-treated at 60 ° C. for 24 hours.
The treated mixture is cooled to room temperature, 1, 1, 1, 3,
5,7,7,7-octamethyltetrasiloxane-3,5-
After adding and mixing 4.0 g of diol, the mixture was left standing at room temperature for 24 hours. Further, heat treatment was carried out at 120 ° C. for 24 hours to obtain surface-treated spherical silicone gel particles. The thus obtained product is hereinafter referred to as spherical silicone gel particle-ΙΙ. In each of Examples 1 to 3 and Comparative Examples 1 to 3 , polyvinyl chloride (TK-1
300 parts by weight of Shin-Etsu Chemical Co., Ltd.), 35 parts of plasticizer (diisononyl phthalate), 3 parts of epoxy soybean oil
Parts, 3 parts of Ba—Zn stabilizer, 2 parts of polymethylmethacrylate (gelling accelerator) and various resin fine particles shown in Table 1 or silicone oil. The obtained composition was kneaded on a 3.5 inch test roll (two rolls) at 150 ° C. for 10 minutes, and then a sheet was prepared by a roll sheet making machine. Then, it is sandwiched between mirror-finished plates and preheated at 170 ° C for 4 minutes, and then pressurized at a pressure of 100 kgf / cm ² for 4 minutes to obtain a size of 120
A sample sheet of × 120 × 1.0 mm was prepared. The appearance of the sample sheet thus obtained, the coefficient of dynamic friction, the contact angle of water,
Also, the slipperiness of each sample was measured by the following method. The results are shown in Table 1.・ Dynamic friction coefficient ・ ・ ・ Measured by Kyowa Interface Science Co., Ltd. ・ Dynamic friction coefficient measuring device under the condition of SUS stainless steel ball with load of 50g and speed of 24cm / sec.・ Contact angle of water: Measured using a contact angle meter manufactured by Kyowa Interface Science Co., Ltd.・ Slidability ・ ・ ・ ・ Stacking the sample sheets, rolling a 500g iron roll on the sheets so that air does not enter between the sheets, and contacting them all over, then place the upper and lower sheets at 180 ° on a plane. The extent of blocking was checked by pulling in the opposite direction and sliding. -Staining resistance A mixture of 30 parts of mulch, 5 parts of cement, 1 part of carbon black, and 5 parts of mineral oil was crushed and kneaded in a ball mill, and 1 g of the mixture was uniformly attached to 100 g of washed and dried sand to form a contaminated material.
A 5 cm x 5 cm test piece of the sample sheet was agitated and brought into contact with the test piece at room temperature for 60 minutes. Then, the degree of contamination on the surface of the test piece was visually observed and evaluated according to the following criteria.

○: Almost no stain ◎: No stain at all ×: Stain on the entire surface

[0036]

[Table 1] (Note) * 1 I: Spherical silicone gel particles I II: Spherical silicone gel particles II * 2 Dimethyl polysiloxane, viscosity (25 ° C) (trade name KF-96, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0037]

EFFECTS OF THE INVENTION Conventionally known methylsilsesquioxane-based powders cannot obtain satisfactory blocking resistance and slidability unless the resin composition is generally added in an amount of 2 wt% or more. As for the molded product, even if the compounding amount of the spherical silicone gel particles as the component (B) is 2% by weight or less, the obtained molded product exhibits good slip properties and blocking resistance.

Since a very small amount of spherical silicone gel particles is sufficient, good transparency can be obtained when the molded product is in the form of a film or sheet. Therefore, it is useful for manufacturing various films and sheets such as a thermal transfer sheet, an agricultural sheet, a food packaging film, and a medical film.

When the composition is molded using a mold, workability is good and productivity is improved because the mold release property between the molded product and the mold is excellent. The slidability, wear resistance, and impact resistance of the obtained molded product itself are also improved. Thus, the composition is suitable for electrical parts, food containers, household products, machine parts,
It is useful for manufacturing various molded products such as cosmetic containers and medical containers.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location // (C08L 101/00 83:06) (72) Inventor Masatoshi Asano Matsuida Town, Usui District, Gunma Prefecture Hitomi No. 1 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Akira Yamamoto Osamu Matsuida Town, Usui District, Gunma Prefecture Hitomi No. 1 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (4)

[Claims] 1. (A) 100 parts by weight of a thermoplastic resin, and (B) formula
(1): [Chemical 1] (In the formula, R represents a methyl group, a trimethylsiloxy group, a vinyl group or a 3,3,3-trifluoropropyl group.)
And an organosiloxane diol represented by the formula (2): (In the formula, R is as described above, and a is 0, 1, 2, or 3.) Average particle surface-treated with at least one selected from the group consisting of organosiloxane diols represented by A thermoplastic resin composition comprising 0.1 to 10 parts by weight of spherical silicone gel particles having a diameter of 0.1 to 5 μm. 2. A molded product obtained by kneading and molding the thermoplastic resin composition according to claim 1. 3. The molded product according to claim 2, which is in the form of a film or a sheet. 4. The molded product according to claim 2, which is molded by a mold.