JPH07122012B2 - Vinyl chloride resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention is excellent in powder flow characteristics which are particularly required in powder (powder) slush molding, and the obtained molded product is superior to conventional products. Also relates to a vinyl chloride resin composition having excellent surface mattability and heat distortion resistance and having an extremely high industrial utility value.

(Prior Art) In recent years, the demand for powdered slush molded products of vinyl chloride resin has been rapidly increasing. This powder (powder) slush molding method supplies synthetic resin powder into a desired molding die, sinters the resin along the inner surface of the molding die to form an integrated fusion product, and collects excess resin powder. It is a method to reuse,
It is required that the synthetic resin composition used for this has excellent powder flow characteristics, and that even the recovered resin composition that has been heated once does not impair the powder flow characteristics. .

(Problems to be Solved by the Invention) However, in the conventional resin composition used for this, when the excessive resin content is repeatedly heated, agglomerated particles grow large each time, and powder flow characteristics are improved. There is a problem that it damages and hinders workability.

In addition, according to this molding method, a finely squeezed pattern is applied to the inner surface of the mold to easily obtain a matt molded product having a high-quality surface. However, repeated use of the mold The inner surface was deteriorated, the matte surface of the molded product was deteriorated, and the cost was increased.

Furthermore, although this molded product has many applications requiring heat distortion resistance, it has not yet achieved the performance sufficient to meet the gist thereof.

Therefore, it is an object of the present invention to prevent the powder flow characteristics from being impaired even when the excess resin that has been heated is repeatedly used in the powder (powder) slush molding process and to be independent of the mold. Another object of the present invention is to obtain a vinyl chloride resin composition capable of imparting excellent surface matting properties and heat distortion resistance to a molded product.

(Means for Solving the Problems) The present invention was found as a result of research for achieving the above object, and (a) one or more kinds of average particle diameters are 30 to 300 μm.
m vinyl chloride resin having an average degree of polymerization of 500 to 2,000, and (b) one or more tetrahydrofuran (hereinafter referred to as THF) insoluble matter of 1 to 50% by weight and a swelling ratio of 5 or more. (C) The average particle size is 2 μm or less and the average degree of polymerization is 500 to 2,0 with respect to the total amount of 100 parts by weight with the vinyl chloride copolymer.
1 to 50 parts by weight of vinyl chloride paste resin of 00, (d) 30 to 150 parts by weight of plasticizer, and (e) 0.1 type of A-type zeolite having an average particle size of 5 μm or less.
The gist of the present invention is that the vinyl chloride resin composition is prepared by blending up to 20 parts by weight.

Explaining this, first, the vinyl chloride resin used as the component (a) in the resin composition of the present invention is a monomer that can be copolymerized with a vinyl chloride monomer, if necessary, such as vinyl acetate. , Ethylene, propylene, vinylidene chloride, acrylonitrile, and a small amount of other acrylic monomers, obtained by polymerizing by bulk polymerization method or suspension polymerization method, all soluble in THF, average particle size 30 ~ 300μm, average degree of polymerization 500 ~ 2,
Those of 000 can be used alone or in combination of two or more.

Here, if the average particle diameter exceeds 300 μm, the melting property becomes poor and high temperature heating is required, and as a result, thermal deterioration is likely to occur. If the particle size is less than 30 μm, the difference in particle size from the vinyl chloride paste resin as the component (c) becomes small and the flow characteristics of the powder are impaired. On the other hand,
If the average degree of polymerization is less than 500, the physical properties such as tensile strength and tear strength are low, and if the average degree of polymerization exceeds 2,000, the workability is significantly deteriorated, which is not preferable.

The vinyl chloride copolymer as the component (b) has an insoluble content in THF of 1 to 50% by weight and a swelling ratio of 5 or more,
It is obtained by copolymerizing a vinyl chloride monomer and a compound having at least two ethylenic double bonds in one molecule, and may be used alone or in combination of two or more.

The compound having an ethylenic double bond is a diene polymer having a plurality of ethylenic double bonds in a molecule having a relatively low molecular weight, such as 1,4-trans-butadiene polymer, 1,4- Cis-butadiene polymer, 1,2
-Butadiene polymer, α, ω-polybutadiene glycol substituted with end groups of polybutadiene and α, ω-
In addition to polybutadiene dicarboxylic acid, 1,4-trans-isoprene homopolymer, 1,4-cis-isoprene homopolymer, chloroprene homopolymer, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, etc. Body compounds, for example, diallyl phthalate, dialkyl malate, diallyl adipate and other diallyl esters, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and other azirii tri (meth) acrylic esters Triallyl cyanurate, divinylbenzene, ethylidene norbornene, dicyclopentadiene, vinyl methacrylate, vinyl crotonate, divinyl adipate and the like are used.

This copolymerization is carried out by a bulk polymerization method or a suspension polymerization method, in which case other monomers copolymerizable therewith, such as vinyl acetate, ethylene, propylene, vinylidene chloride, acrylonitrile, and other acrylic monomers are used. It is safe to use a small amount of.

Although the desirable copolymerization ratio of the compound having an ethylenic double bond to vinyl chloride is individually determined according to the kind of the compound having an ethylenic double bond, it cannot be stated uniformly. , Any of the produced copolymers has an insoluble content in THF of 1 to 50% by weight.
Therefore, it is necessary to satisfy the requirement that the swelling ratio is 5 or more. If the content of insolubles in THF is less than 1% by weight, the effect of improving the powder fluidity during molding, the matteness of the molded product, and the heat distortion resistance is small, and conversely if it exceeds 50% by weight, The workability is remarkably deteriorated and the molding work becomes difficult. On the other hand, when the swelling ratio with respect to THF is less than 5, the effect of improving the powder fluidity at the time of molding, the matting property of the molded product, the heat distortion resistance, and the like becomes small.

In the present invention, the insoluble matter (or soluble matter) and the swelling ratio in THF are defined by the values measured under the following conditions.

Measurement of insoluble matter (or soluble matter) and swelling ratio in THF: Put 1 g of sample into a 100 ml colorimetric tube, add 80 ml of THF thereto, and shake well at room temperature. Put the colorimetric tube in a hot water bath at 75-85 ° C and shake with heating. Do this for 5 minutes. Cool to room temperature, add THF to 100 ml marked line, and shake well again. After standing overnight, read the volume of the THF insoluble portion, divide this value by the apparent volume of the resin before adding THF, and use the obtained value as the swelling ratio.

Next, remove the supernatant with a 10 ml pipette, remove the THF by dryness, precisely weigh the resin content (W), divide 10 times that by the initial sample amount of 1 g, and multiply this quotient by 100 The content was soluble. The insoluble matter is calculated by the following formula.

Here, the mixing ratio of the component (a) and the component (b) is It is desirable that the value satisfies the relationship of. In this formula, if it exceeds 95/5, there is no effect of heat distortion resistance and surface matting, and if it is less than 50/50, the meltability when processing the vinyl chloride resin composition of the present invention deteriorates, which is not preferable. .

The vinyl chloride paste resin as the component (c) has an average degree of polymerization obtained by an emulsion polymerization method or a solution polymerization method.
The average particle size is 500 to 2,000 and the average particle size is 2 μm or less. Those having an average degree of polymerization outside this range are unsuitable for the present invention because of the same reason as that of the resin as the component (a), and those having an average particle size of more than 2 μm do not improve the powder fluidity. .

When the vinyl chloride paste resin is polymerized, the vinyl chloride monomer used may be used in combination with a small amount of a monomer copolymerizable therewith.

There is no particular problem with the plasticizer as the component (D) as long as it has been conventionally used for the production of a flexible molded product of vinyl chloride resin, and it includes phthalates such as dibutylphthalate and di- (2-ethylhexyl) phthalate. Examples thereof include acid esters; alkyl esters of aliphatic polybasic acids such as dioctyl adipate and dioctyl sebacate; alkyl phosphate esters such as tricresyl phosphate; and other low-polymerization polyesters.

The type A zeolite as the component (e) is not particularly limited as long as it has a commercially available average particle size of 5 μm or less. When the average particle size exceeds 5 μm, the dispersibility is deteriorated, the appearance is impaired, and the improvement of the powder flow characteristics when subjected to repeated heat cannot be expected.

The vinyl chloride resin composition of the present invention has been described above in (a).
~ The main component is the component (e),
The mixing ratio of these components is 100 parts by weight of the total amount of the vinyl chloride resin as the component (a) and the vinyl chloride copolymer as the component (b), and the vinyl chloride resin as the component (c). It is necessary to use 1 to 50 parts by weight of the paste resin, 30 to 150 parts by weight of the plasticizer as the component (d), and 0.1 to 20 parts by weight of the A-type zeolite as the component (e).

This is because if the amount of the component (C) is less than 1 part by weight, stickiness becomes large and the workability deteriorates, and if it exceeds 50 parts by weight, the dispersibility deteriorates and there is a problem in economic efficiency. Further, if the amount of component (d) is less than 30 parts by weight, the physical properties such as tensile strength and tear strength are deteriorated in addition to the decrease in hardness, which is not preferable, and if it exceeds 150 parts by weight, the powder flow characteristics are remarkably deteriorated. Processing becomes difficult and the effect of the present invention cannot be obtained. Further, if the amount of the component (e) is less than 0.1 parts by weight, the effect of the present invention is too small to obtain the effect of the present invention, and if it exceeds 20 parts by weight, physical properties such as hardness, tensile strength and tear strength are deteriorated, which is not preferable.

The composition of the present invention further comprises a stabilizer, if necessary.
A lubricant, a release agent, a filler, a colorant, an antioxidant, an ultraviolet absorber, and various other additives may be added.

(Examples) Hereinafter, specific embodiments of the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to the description of the following Examples without departing from the scope of the invention.

16 types of mixtures of Examples 1 to 8 and Comparative Orders 1 to 8 shown in the attached table were prepared using the following materials.

Vinyl chloride resin: TK-700 (THF insoluble matter: 0%, suspension polymerized product, average particle size:
Approximately 150 μm, average degree of polymerization: 680, manufactured by Shin-Etsu Chemical Co., Ltd. TK-800 (THF insoluble matter: 0%, suspension polymerized product, average particle size:
Approximately 150 μm, average degree of polymerization: 830, the same) Vinyl chloride copolymer: GR-1300 (THF insoluble matter: 25% by weight, swelling and swelling ratio: 15, suspension polymerization product, average polymerization of THF insoluble matter) Degree: 1,100, same) Vinyl chloride paste resin: (Average particle size: 1 μm or less, average degree of polymerization: 1,500, commercial product) Plasticizer: DL-911P (phthalate ester type, manufactured by Shell Chemical Co., Ltd.) A-type zeolite: (Average particle size: 2.2-2.5 μm, synthetic calcium aluminum silicate, CaO content: 11.0% Al ₂ O ₃ content: 27.0%, particle size 325 mesh all-through, commercial product) Stabilizer: epoxy Soybean oil barium / zinc stabilizer Stabilize the vinyl chloride resin (a) component, vinyl chloride copolymer (b) component and barium / zinc stabilizer into a Henschel mixer and heat. While stirring, mix. When the material temperature reaches 80 ° C., the total amount of the epoxidized soybean oil and the half amount of the plasticizer of the component (d) are added, and then the mixture is heated and stirred while mixing. When the material temperature reaches 100 ° C, the remaining plasticizer is added, and the mixture is heated and stirred until the material temperature reaches 120 ° C. When it reaches 120 ° C., it is cooled by passing water, and when it becomes 40 ° C. or less, the vinyl chloride paste resin as the component (c) and the A-type zeolite as the component (e) are charged and mixed with stirring. After the mixing was completed, the obtained mixture was discharged from the mixer and passed through a JIS standard passing 40 mesh sieve to obtain each powder compound.

The powder flow characteristics and processability were evaluated for each of the following methods.

Flow characteristics of the compound: Using the bulk specific gravity measuring device of the vinyl chloride resin test method (JIS K-6721) at the following temperatures and conditions, the dropping time of 100 ml of the composition obtained by the bulk specific gravity measuring operation was repeated three times. It measured and calculated | required the average value.

Condition I: Measured after standing for 24 hours in a constant temperature and humidity condition of 20 ± 2 ° C and humidity of 60 ± 2% after creating the compound.

Condition II: 200 g of the remaining compound according to Condition I is about 101,5
Spread on a 00mm ² aluminum bat, 20 ± 2 ℃, humidity 60 ± 2
% After being left for 2 hours at a constant temperature and humidity, then left in an oven heated to 140 ° C for 4 minutes and then allowed to cool at room temperature for 30 minutes for measurement.

Condition III: Collect the remaining compound according to Condition II,
After standing in an oven heated to 0 ° C for 4 minutes, let stand for 30 minutes to cool at room temperature.

Condition IV: Measured by collecting the remaining compound according to condition III and further performing the same treatment as condition III.

Condition V: Measured by collecting the remaining compound according to condition IV and further performing the same treatment as condition III.

Condition VI: Measured by collecting the remaining compound according to condition V and further performing the same treatment as condition III.

Compound processability: Spread each compound obtained in Condition VI on an iron plate (15 cm x 25 cm, mold that has been sandblasted and embossed on the surface) heated to 210 ° C, leave it for 20 seconds, and then oven at 270 ° C. The sheet was left standing for 50 seconds, formed into a sheet, immediately cooled with water, and removed from the mold. The thickness was reproducible and the state of generation of compound aggregates was evaluated comprehensively according to the following criteria.

Very good ……… ◎ Good ………… Slightly good …… △ Poor workability ………… × In addition, 210 each compound obtained under the conditions I and VI was used.
A steel plate heated to ℃ is coated with a thickness of about 2 mm, put it in a heating furnace whose internal temperature is maintained at 270 ℃, and sinters it for 50 seconds. The resulting molded product is subjected to a tensile test (JIS K 7113). Tear test (JIS K 6301) Heat aging test (JIS K 7212) Hardness (JIS K 6301) Physical property tests were conducted and the measured values were compared, but no significant difference was found between them.

Further, each powder compound described above was heated and sintered by the same method, and the obtained sheet was evaluated for surface matting property and heat distortion resistance by the following methods.

Surface matting property: The surface of each obtained sheet was observed and evaluated according to the following criteria.

Very good surface mattness. ……… ◎ Good matte surface. ……… ○ There is a little gloss, and the surface mattness is somewhat difficult. ……… △ Strong gloss and no matte surface. ……… × Thermal deformation resistance: Sintered molded product was lined with urethane foam to a thickness of 10 mm, and four test pieces of 250 mm × 250 mm were cut from this, and 10 mm on each edge on the vinyl film surface side. Write a square reference line parallel to each inside. The distance between the two parallel lines that face each other in the vertical and horizontal directions is accurately measured at each of at least four points, and the average value of each is determined to be the original size. This is heated at 120 ° C. for 1 hour and 96 hours, respectively, and then allowed to cool at room temperature for 1 hour. After that, the distance between the two parallel lines which face each other in the vertical and horizontal directions is measured again in the same manner as above, the average value of each is obtained and compared with the original size, and the average value of the deformation rates of both is taken as the heat deformation resistance. This value was expressed as follows.

Less than 1% ………… ○ More than 1% ………… × The above results are summarized in the table.

(Effects of the Invention) The vinyl chloride resin composition according to the present invention has not only powder flow characteristics (workability) when repeatedly heated, but also matting properties, heat distortion resistance and the like of the obtained molded product. Since the composition is remarkably improved, this composition is suitable for powder slush molding, and its industrial utility value is extremely high.

The molded product thus obtained is extremely useful as, for example, automobile interior parts and materials, particularly instrument panels, meter boxes, console boxes, door trims, crash pads, headrests, armrests, glove boxes, shift knobs and the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hirokazu Seki 2-9, Higashizakashita, Itabashi-ku, Tokyo Inside Pigment Co., Ltd., Japan Pigment Co., Ltd. (56) References JP-A-58-198555 (JP, A) JP-A-58-152040 (JP, A) JP-A-1-156357 (JP, A) JP-A-59-74146 (JP, A) JP-A-59-66440 (JP, A)

Claims (2)

[Claims] 1. A vinyl chloride resin having an average particle size of 30 to 300 μm and an average degree of polymerization of 500 to 2,000, and (b) one or two or more types of tetrahydrofuran. (C) The average particle size is 2 μm or less and the average degree of polymerization is 500 to 2, with respect to 100 parts by weight of the total amount of the vinyl chloride-based copolymer having a dissolved content of 1 to 50% by weight and a swelling ratio of 5 or more. 0
1 to 50 parts by weight of vinyl chloride paste resin of 00, (d) 30 to 150 parts by weight of plasticizer, and (e) 0.1 type of A-type zeolite having an average particle size of 5 μm or less.
~ 20 parts by weight of a vinyl chloride resin composition. 2. A powder slush molded product comprising the vinyl chloride resin composition according to claim 1.