JPH07122010B2 - 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 particularly required in powder (powder) slush molding, and the obtained molded product is more excellent than conventional products. The present invention relates to a vinyl chloride resin composition having an extremely high industrial utility value, which is excellent in surface mattability and heat distortion resistance.

(Prior Art) In recent years, the demand for vinyl chloride resin-based powder (powder) slush molded products has rapidly increased. The koho powder (powder) slush molding method is a method in which a synthetic resin is sintered along the inner surface of a desired molding die to form an integrated fusion product. The synthetic resin composition used for this Is required to have excellent powder flow characteristics, particularly the powder flow characteristics of the recovered resin composition once heated.

(Problems to be solved by the invention) Particularly, in the current molding process, a method of recovering an excessive amount of the composition that has been heated and reusing it in the next molding step is used. It has been a problem in the molding process that it is repeatedly heated, and the grain size grows larger each time, impairing the powder flow characteristics.

In addition, the molded product obtained by this molding method is still insufficient in spite of the large number of applications requiring a high-grade texture with a matt surface and heat deformation characteristics. There are many.

In particular, the currently used matting method was achieved by applying a fine drawing pattern to the inner surface of the molding die.
In addition to repeated use of the mold, deterioration of the matte property of the surface of the molded product due to deterioration of the inner surface of the mold poses a problem and also causes a cost increase.

Therefore, it is an object of the present invention that, in the powder (powder) slush molding process, even if the heated excess composition is repeatedly used, the powder flow characteristics are not impaired, and the composition does not depend on the mold. It is intended to obtain a vinyl chloride resin composition which can impart excellent surface matting properties and heat distortion resistance to a molded product without the need.

(Means for Solving the Problems) The present invention has been found as a result of research conducted to achieve the above-mentioned object. (A) Insoluble matter in Tesla hydrofuran is 1 to 50% by weight, and swelling ratio is , 5.0 or more, average degree of polymerization of dissolved components is 500
Vinyl chloride-based copolymer obtained by suspension polymerization of 1 or 2 or more: 100 parts by weight, (b) having an average particle size of 2 μm or less, and having an average degree of polymerization of 500 to 2
000 vinyl chloride paste resin: 1 to 30 parts by weight, (c) plasticizer: 30 to 150 parts by weight, (d) synthetic calcium carbonate having an average particle size of 0.1 μm or less:
The gist is that the vinyl chloride resin composition comprises 0.1 to 10 parts by weight.

To explain this, first, the vinyl chloride-based copolymer used as the component (a) in the resin composition of the present invention is
The vinyl chloride-based copolymer contains a specific amount of tetrahydrofuran (hereinafter simply referred to as THF) insoluble matter and has a swelling ratio above a specific range. Those obtained by copolymerizing at least two compounds having an ethylenic double bond can be used as one kind or as a mixture of two or more kinds.

The compound having an ethylenic double bond used herein is a diene-based polymer having a plurality of ethylenic double bonds in a molecule having a relatively low molecular weight, for example, 1,
The terminal groups of 4-trans-butadiene polymer, 1,4-cis-butadiene polymer, 1,2-butadiene polymer and polybutadiene were substituted. α, ω-polybutadiene glycol and α, ω-polybutadiene dicarboxylic acid, 1,
4-trans-isoprene homopolymer, 1,4-cis-isoprene homopolymer, chloroprene homopolymer, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer and the like are used, and polyfunctional monomer compounds such as diallyl phthalate. , Diallyl malates, diallyl esters such as diallyl adipate, di- or tri (meth) acrylic esters such as ethylene glycol diacrylate, trimethylolpropane triacrylate, triallyl cyanurate, divinylbenzene, ethylidene norbornene, dicyclopentadiene, Vinyl methacrylate, vinyl crotonate, divinyl adipate, etc. are used.

This copolymerization is carried out by a suspension polymerization method, in which case a small amount of other monomers copolymerizable therewith, such as vinyl acetate, ethylene, propylene, vinylidene chloride, acrylonitrile, and other acrylic monomers are used in combination. You can do it.

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. In any of the produced copolymers, the content of insoluble matter in THF is 1 to 50% by weight, preferably 7 to 30% by weight, the swelling ratio is 5 or more, and the average degree of polymerization of the soluble matter is 500 to 1500. There is a need to. 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.
Even when the swelling ratio with respect to THF is less than 5, similarly, the effect of improving the powder fluidity during molding, the matteness of the molded product, the heat distortion resistance, and the like becomes small. Further, when the average degree of polymerization of the dissolved component is less than 500, the mechanical strength of the obtained molded article decreases, and when it exceeds 1500, the processability decreases.

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 the 100 ml marked line, and shake well again. After standing overnight, read the volume of the THF insoluble part,
This is divided by the apparent volume of the resin before adding THF, and the obtained value is the swelling ratio.

Then, 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 by 100 to obtain the THF value. It was taken as the soluble component. Insoluble matter is calculated by the following formula.

The vinyl chloride paste resin as the component (b) has an average degree of polymerization of 50, which is obtained by an emulsion polymerization method, a solution polymerization method, or the like.
The average particle size is 0 to 2000 and the average particle size is 2 μm or less. If the average degree of polymerization of the obtained resin is less than 500, the required properties such as tensile strength and tear strength are not satisfied, and if it exceeds 2000, the processability is deteriorated, and if the average particle size exceeds 2 μm, it is powder. It is unsuitable for the present invention because the fluidity is not improved. The vinyl chloride-based paste resin is a vinyl chloride monomer used therein, which is similar to the component (a) and can be copolymerized therewith, for example, vinyl acetate,
A small amount of ethylene, propylene, vinylidene chloride, acrylonitrile or the like may be used in combination without any problem.

There is no particular problem with the plasticizer as the component (c) as long as it has been conventionally used in the production of flexible molded articles of vinyl chloride resin, and examples thereof include dibutyl phthalate and di- (2
-Ethylhexyl) phthalate and other phthalates; dioctyl adipate, dioctyl sebacate and other aliphatic polybasic acid alkyl esters; tricresyl phosphate and other phosphoric acid alkyl esters; examples thereof include low-polyesters To be done.

The synthetic calcium carbonate having an average particle diameter of 0.1 μm or less as the component (d) is mainly obtained by the carbon dioxide gas reaction method and the soluble salt reaction method, and has a uniform particle shape as compared with natural calcium carbonate, Although it has the advantage that the variation in particle size is small, when the average particle size exceeds 0.1 μm, the dispersibility deteriorates and the appearance is impaired. I can't hope for improvement.

These 4 constituting the vinyl chloride resin composition of the present invention
The blending ratio of the components is 1 to 30 parts by weight (preferably 5 to 20 parts by weight) of the vinyl chloride paste resin as the component (b) with respect to 100 parts by weight of the vinyl chloride copolymer as the component (a). , 30 to 150 parts by weight (preferably 50 to 100 parts by weight) of the plasticizer as the component (c), and 0.1 to 10 of the synthetic calcium carbonate having an average particle diameter of 0.1 μm or less as the component (d).
It is necessary to adjust the amount by weight (preferably 0.1 to 4 parts by weight). This is because if the amount of component (b) is less than 1 part by weight, stickiness becomes large and workability becomes difficult, and if it exceeds 30 parts by weight, dispersibility deteriorates and there is a problem in economy. Also, the component (c) is 30
If it is less than 1 part by weight, it is not preferable because the physical properties such as tensile strength and tear are deteriorated in addition to the decrease in hardness, and if it exceeds 150 parts by weight, the powder flow characteristics are remarkably deteriorated and the effect of the present invention is obtained. I can't. Furthermore, the component (d) is 0.1
If it is less than 10 parts by weight, the effect of the present invention cannot be obtained, and if it exceeds 10 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.
As in the conventional case, various additives such as a lubricant, a release agent, a filler, a coloring agent, other antioxidants, and an ultraviolet absorber 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.

Nine kinds of mixtures of Examples 1 to 7 and Comparative Examples 1 and 2 shown in the attached table were prepared using the following materials.

Vinyl chloride copolymer: TK-700 (THF insoluble matter: 0%, swelling ratio: 0, THF soluble matter average degree of polymerization: 680, suspension polymer, Shin-Etsu Chemical Co., Ltd.) TK-800 ( THF insoluble matter: 0%, swelling ratio: 0, THF soluble matter: average degree of polymerization: 830, suspension polymer, same as above GR-800 (THF insoluble matter: 20% by weight, swelling ratio: 5.0, THF soluble matter) GR-1300 (THF insoluble matter: 25% by weight, swelling ratio: 15.0, THF)
Dissolved content Average degree of polymerization: 1100, Suspension polymerized product, same as above) Vinyl chloride paste resin: (Average particle size: 1 μm or less, average degree of polymerization: 1500) Plasticizer: DL-911P (phthalate ester type, shell) Chemicals Co., Ltd. Stabilizer: Epoxidized soybean oil Barium / zinc stabilizer Synthetic calcium carbonate: Shirakane CC (average particle size 0.04 μm, Shiraishi Calcium Co., Ltd.)
White Sinter CCR (average particle size 0.08 μm, same as above) Add the (a) component vinyl chloride resin barium / zinc stabilizer to the Henschel Super Mixer and stir and mix 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 (c) are added, and the mixture is heated with stirring and mixing.

When the material temperature reaches 100 ° C, the remaining amount of the plasticizer is added, and the mixture is further heated and stirred until the material temperature reaches 120 ° C. When the material temperature reaches 120 ° C, cool it by passing water,
When the material temperature becomes 40 ° C. or lower, the vinyl chloride paste resin as the component (b) and the synthetic calcium carbonate as the component (d) are charged and mixed with stirring.

After mixing, discharge the obtained mixture from the mixer and
Each powder compound was obtained by passing through a 40 mesh sieve that passed the S standard.

The powder flow characteristics and processability were evaluated for each of the following methods. Further, this compound was coated on an iron plate heated to 210 ° C. to a thickness of about 2 mm, transferred to a heating furnace whose internal temperature was adjusted to 300 ° C., and sintered for 50 minutes.
The matte surface and heat distortion resistance of the obtained sheet were evaluated by the following methods, and the results are shown in the table.

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. The measurement was performed three times to obtain an average value, and the results are also shown in the table.

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 an aluminum pad of 00mm ² , 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,
Measured by leaving it in an oven heated to 0 ° C for 4 minutes and then allowing it to cool at room temperature for 30 minutes.

Condition IV: Measured by collecting the remaining compound according to condition III, and further applying 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 300 ° 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 …… × Surface matteness: The surface of each of the obtained sheets was observed and evaluated according to the following criteria.

Good surface mattness. ……… ○ There is a little gloss, and the surface mattness is somewhat difficult. ……… △ Strong gloss and no matte surface. ……… × Thermal deformation resistance: Sintered molded product is lined with urethane foam to a thickness of 10 mm,
Take four 250 mm x 250 mm test pieces and write a reference line parallel to the edge 10 mm inside from each side on the vinyl film surface side. Accurately measure the distance between the two parallel lines at least four places,
The average value of each length and width is calculated and used as the original size. This 12
After heating at 0 ° C. for 1 hour and 96 hours, it is left to cool at room temperature for 1 hour. After that, the interval between the two parallel lines should be at least 4 again.
Accurately measure at more than one place, obtain the average value of each length and width and compare with the original size, and make the difference the heat distortion resistance. Those having an average deformation rate of less than 1% were evaluated as ◯, and those having an average deformation rate of 1% or more were evaluated as x.

Various physical property tests of sintered molded products: In the above-mentioned evaluation method of on-powder powder flow characteristics, each compound obtained under conditions I and VI was heat-sintered by the above-mentioned method, and the molded product obtained was stretched. Test (JIS K 7113) Tear test (JIS K 6301) Heat aging test (JIS K 7212) Hardness (JIS K 6301) Comparisons were made by various physical property tests, but no significant difference was found for each measured value. .

(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 (56) References JP-A-59-120645 (JP, A) JP-A-56-125443 (JP, A) JP-A-58-198555 (JP, A) JP-A-58- 152040 (JP, A)

Claims (2)

[Claims] 1. A suspension polymerization of one or more of (a) insoluble matter in tetrahydrofuran of 1 to 50% by weight, swelling ratio of 5.0 or more, and average degree of polymerization of dissolved matter of 500 to 1500. Obtained vinyl chloride-based copolymer: 100 parts by weight, (b) average particle size of 2 μm or less, average degree of polymerization of 500 to 2
000 vinyl chloride paste resin: 1 to 30 parts by weight, (c) plasticizer: 30 to 150 parts by weight, (d) synthetic calcium carbonate having an average particle size of 0.1 μm or less:
A vinyl chloride resin composition comprising 0.1 to 10 parts by weight. 2. A powder slush molded product comprising the vinyl chloride resin composition according to claim 1.