JPH07122009B2 - 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 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 It is required that the powder flow characteristics, in particular, the recovered resin composition once heated be excellent in the powder flow characteristics.

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

In addition, the molded product obtained by this molding method is still insufficient in many cases in spite of the large number of applications in which the surface gloss is required to have a high-grade texture and thermal deformation characteristics. .

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 for achieving the above-mentioned object, and (a) the insoluble content in 1 or 2 or more kinds of tetrahydrofuran is 1 to 50% by weight. % Vinyl chloride copolymer having a swelling ratio of 5.0 or more: 100 parts by weight, (b) an average particle diameter of 2 μm or less, and an average degree of polymerization of 500 to 2
000 vinyl chloride paste resin: 1 to 50 parts by weight, (c) plasticizer: 30 to 200 parts by weight, (d) hydrous silicic acid or silicic acid having an average particle size of 5 μm or less: 0.1 to 30 parts by weight, The gist of the present invention is to provide a vinyl chloride resin composition comprising

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. The thing obtained by copolymerizing with the compound which has at least 2 ethylenic double bond in it can be used as 1 type or 2 or more types of mixture.

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, such as 1,4-trans-butadiene polymer, 1,4-cis-butadiene polymer, 1,2-butadiene polymer,
Α, ω-polybutadiene glycol and α, ω-polybutadiene dicarboxylic acid, 1,4-trans-isoprene homopolymer, wherein the end groups of polybutadiene are substituted,
1,4-cis-isoprene homopolymer, chloroprene homopolymer, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer and the like are used, as well as polyfunctional monomer compounds such as diallyl phthalate, diallyl malate and diallyl adipate. Diallyl esters, ethylene glycol diacrylate, di- or tri (meth) acrylic esters such as trimethylolpropane triacrylate, triallyl cyanurate, divinylbenzene, ethylidene norbornene, dicyclopentadiene, vinyl methacrylate, vinyl crotonic acid, Divinyl adipate or the like is used.

This copolymerization is carried out by a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, etc., in which case other monomers copolymerizable therewith, for example, vinyl acetate, ethylene, propylene, vinylidene chloride are used. , Acrylonitrile, and other acrylic monomers may be used in a small amount 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, the requirement that the swelling ratio is 5 or more needs to be satisfied. 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, 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.

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 part, divide this by the apparent volume of the resin before adding THF, and take the obtained value as 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-based 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. In this vinyl chloride paste resin, the vinyl chloride monomer used therein may be used in a small amount in combination with a small amount of a monomer similar to the component (a) and copolymerizable therewith.

There is no particular problem with the plasticizer as the component (C) as long as it has been conventionally used in the production of soft molded vinyl chloride resins, and examples thereof include dibutyl phthalate and di- (2
-Ethylhexyl) phthalate and other phthalic acid esters; dioctyl adipate, dioctyl sebacate and other aliphatic polybasic acid alkyl esters; tricresyl phosphate and other phosphoric acid alkyl esters; It

The hydrous silicic acid or silicic acid anhydride as the component (d) 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 deteriorates, not only the appearance is impaired, but also the improvement of the powder flow characteristics when receiving repeated heat cannot be expected.

These 4 constituting the vinyl chloride resin composition of the present invention
The mixing ratio of the components is 1 to 50 parts by weight of the vinyl chloride paste resin as the component (b), and the plasticizer as the component (c) with respect to 100 parts by weight of the vinyl chloride copolymer as the component (a). To 30 to 200 parts by weight, and (d) hydrous silicic acid or silicic acid anhydride as the component (d) to 0.1 to 30 parts by weight. If the amount of the component (b) is less than 1 part by weight, the tackiness is large and the workability becomes difficult, and if it exceeds 50 parts by weight, the dispersibility is deteriorated and there is a problem in economical efficiency. If the content of (C) is less than 30 parts by weight, the physical properties such as tensile strength and tear strength will decrease in addition to the decrease in hardness, and it is not preferable. It is difficult to obtain the effect of the present invention. Furthermore, (d) component is 0.1
If it is less than 30 parts by weight, the effect of the present invention cannot be obtained, and if it exceeds 30 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 prior art, 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: ∞, average degree of polymerization: 680, manufactured by Shin-Etsu Chemical Co., Ltd.) TK-800 (THF insoluble matter: 0%, Swelling ratio: ∞, average degree of polymerization: 830, same) GR-800 (THF insoluble matter: 20% by weight, swelling rate: 5.0, average degree of polymerization 760, same) GR-1300 (THF insoluble matter: 25) % By weight, swelling ratio: 15.0, average degree of polymerization: 1100, the same) Vinyl chloride paste resin: P-410 (manufactured by Mitsubishi Kasei Vinyl Co., Ltd., average particle size: 1 μm)
Below, average degree of polymerization: 1500) Plasticizer: DL-911P (Phthalate ester type, manufactured by Shell Chemical Co., Ltd.) Stabilizer: Epoxidized soybean oil Barium / zinc type stabilizer Silic acid: Syloid ^# 74 ( Average particle size 4 μm, made by Fuji Davison Chemical Co., Ltd. Aerosil 200 (average particle size 12 mμm, made by Nippon Aerosil Co., Ltd.) Each mixture is heated to 110 ° C. with a super mixer and stirred, then cooled by water flow, JIS The powder compound composition was obtained by passing through a 40 mesh sieve that passed the specifications.
The powder flow characteristics and processability were evaluated for each of the following methods. Furthermore, this composition is applied on an iron plate to a thickness of about 2 m.
After coating to m, it was transferred to a heating furnace having a constant temperature and sintered for 2 minutes. The obtained soot was evaluated for surface mattability and heat distortion resistance by the following methods, and the respective results are shown in the table.

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. The average value was obtained by measurement, 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 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,
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 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 workability: Comprehensively evaluated from the reproducibility of the thickness when molding the compound treated with the condition VI and the occurrence of lumps due to lumps, and from the one with a low degree of problem occurrence, ○ <△
Evaluation was made based on <x.

Surface matting property: The surface of each obtained sheet 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-described method for evaluating the fluidity characteristics of the compound, each compound obtained under the conditions I and VI was heat-sintered by the method described above, and the molded product obtained was subjected to a tensile test (JIS K 7113) Tear test (JIS K 6301) Heat aging test (JIS K 7212) Hardness (JIS K 6301) was compared by various physical property tests, but no significant difference was found in 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) Reference JP 58-198555 (JP, A) JP 58-152040 (JP, A) JP 59-120645 (JP, A) JP 56-131651 (JP , A) JP-A-56-125443 (JP, A)

Claims (2)

[Claims] 1. A vinyl chloride copolymer having an insoluble content of 1 to 50% by weight in tetrahydrofuran of 1 or 2 or more and a swelling ratio of 5.0 or more: 100 parts by weight, and (b) an average particle. Diameter less than 2μm, average degree of polymerization is 500-2
000 vinyl chloride paste resin: 1 to 50 parts by weight, (c) plasticizer: 30 to 200 parts by weight, (d) hydrous silicic acid or silicic acid having an average particle size of 5 μm or less: 0.1 to 30 parts by weight, A vinyl chloride resin composition comprising: 2. A powder slush molded product comprising the vinyl chloride resin composition according to claim 1.