JPH07122011B2 - 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 an extremely high value for industrial use, which has excellent surface matting properties and heat distortion resistance.

(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 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, by applying a fine drawing pattern to the inner surface of the mold, it is possible to easily obtain a matte molded product with a high-quality surface. And deteriorated the mattness of the surface of the molded product, which was a cause of cost increase.

Furthermore, although this molded product has many applications requiring heat distortion resistance, it has not been possible to obtain sufficient performance to meet the demand.

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 heat distortion resistance to a molded article.

(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 200 parts by weight of plasticizer, and (e) 0.1 to 10 parts by weight of synthetic calcium carbonate having an average particle size of 0.1 μm or less are blended. The gist of the present invention is that it is a vinyl chloride resin composition.

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 as one kind or as a mixture of two or more kinds.

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, those having an average degree of polymerization of less than 500 have poor physical properties such as tensile strength and tear strength, and those having an average degree of polymerization of more than 2,000 have a markedly poor processability, 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 can 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-
Polybutadienecarboxylic acid, 1,4-trans-isoprene homopolymer, 1,4-cis-isoprene homopolymer, chloroprene homopolymer, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, etc. are used, and polyfunctional monomer Compounds such as diallyl phthalate, diallyl malate, diallyl adipate and other diallyl esters, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and other di- or tri (meth) acrylic esters, triallyl sialic acid Nurate, divinylbenzene, ethylidene norbornene, dicyclopentadiene, vinyl methacrylate, vinyl crotonic acid, 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 another monomer capable of being copolymerized therewith,
For example, a small amount of vinyl acetate, ethylene, propylene, vinylidene chloride, acrylonitrile, and other acrylic monomers may be used together.

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 condition 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 powder fluidity during molding, matteness of the molded article, and heat distortion resistance is small, and 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 with respect to 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 part,
This value is divided by the apparent volume of the resin before adding THF, and the obtained value is taken 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 content is calculated by the following formula.

The mixing ratio of this (a) component and (b) component 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 property, and if it is less than 50/50, the meltability when the vinyl chloride resin composition of the present invention is processed is deteriorated, which is preferable. Absent.

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. Here, 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 component (a), and those having an average particle size of more than 2 μm do not improve the powder fluidity.

In this vinyl chloride paste resin, a small amount of a monomer copolymerizable with the vinyl chloride monomer used in the polymerization may be used in combination.

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 this includes phthalates such as dibutyl phthalate and di- (2-ethylhexyl) phthalate. Examples thereof include acid esters; alkyl esters of aliphatic polybasic acids such as dioctyl adipate and dioctyl sebacate; phosphoric acid alkyl esters such as tricresyl phosphate; and their low polymerization degree polyesters.

(E) Synthetic calcium carbonate having an average particle diameter of 0.1 μm or less as a component is mainly obtained by a carbon dioxide gas reaction method or a soluble salt reaction method, and has a more uniform particle shape than natural calcium carbonate. It has the advantage of small variation in diameter, but here the average particle size is 0.1μ.
When it exceeds m, not only the dispersibility deteriorates and the appearance is impaired, but also the improvement of the powder flow characteristics upon repeated heat application cannot be expected.

These 5 constituting the vinyl chloride resin composition of the present invention
The blending ratio of the components is the total amount of the vinyl chloride resin as the component (a) and the vinyl chloride copolymer as the component (b).
To 100 parts by weight, 1 to 50 parts by weight of the vinyl chloride paste resin as the component (c), 30 to 200 parts by weight of the plasticizer as the component (d), and 0.1% of the synthetic calcium carbonate as the component (e). Must be ~ 10 parts by weight.

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 content of (d) component 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 200 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 10 parts by weight, the physical properties such as hardness, tensile strength and tear strength are deteriorated.

The composition of the present invention may further contain a stabilizer, if necessary.
A lubricant, a release agent, a filler, a coloring agent, an antioxidant, an ultraviolet absorber, and various additives thereof 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 kinds of mixtures of Examples 1 to 8 and Comparative Examples 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:
About 150 μm, average degree of polymerization: 830, the same) Vinyl chloride copolymer: GR-1300 (THF insoluble matter: 25% by weight, swelling ratio: 15, suspension polymer, average degree of polymerization of THF insoluble matter) : 1100, same as before) 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.) Synthetic Calcium carbonate: Shiragika CC (average particle size: 0.04 μm, manufactured by Shiraishi Calcium Co., Ltd.) Nichigana CCR (average particle size: 0.08 μm, the same as before) Stabilizer: Epoxidized soybean oil Barium / zinc stabilizer Henschel The vinyl chloride resin as the component (a), the vinyl chloride copolymer as the component (b) and the barium / zinc stabilizer are charged into a mixer and mixed with stirring while heating. 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 the temperature reaches 120 ° C, it is cooled by passing water, and when it becomes 40 ° C or lower, the vinyl chloride paste resin as the component (c) and the synthetic calcium carbonate as the component (e) are added 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 of each of these were evaluated by the following methods.

Powder flow characteristics of the compound: Using the vinyl chloride resin test method (JIS K-6721) bulk specific gravity measuring device at each of the following temperatures and conditions, measure the drop time of 100 ml of the composition obtained by the bulk specific gravity measuring operation. It measured 3 times 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
Measured by leaving it in a constant temperature and humidity of ℃ for 2 hours, then in an oven heated to 140 ℃ for 4 minutes, and then letting it cool at room temperature for 30 minutes.

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, molded into a sheet, immediately cooled with water and removed from the mold, and the following criteria were used for comprehensive evaluation based on the reproducibility of the thickness and the state of formation of compound aggregates.

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 Japan Pigment Co., Ltd. Tokyo factory (56) Reference JP-A-58-152040 (JP, A) JP-A-58-198555 (JP, A) JP-A-1-156357 (JP, A) JP-A-59-74146 (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 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 200 parts by weight of plasticizer, and (e) 0.1 to 10 parts by weight of synthetic calcium carbonate having an average particle size of 0.1 μm or less are blended. A vinyl chloride resin composition comprising: 2. A powder slush molded product comprising the vinyl chloride resin composition according to claim 1.