JPS6037784B2 - Vinyl chloride copolymer vacuum molded product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinyl chloride copolymer-based vacuum molded product, and more specifically, the present invention uses a vinyl chloride resin composition using a special vinyl chloride copolymer to improve luster. Concerning vacuum-formed products that have been erased and have a slight loss of luster after vacuum forming.

For example, an automobile dashboard made of vinyl chloride resin (hereinafter sometimes referred to as vinyl chloride resin) is a matte product usually manufactured by a vacuum forming method. The reason for vacuum forming is
This is because the mold changes frequently and is suitable for mass production, and the reason why it is matte is to protect the eyes of the driver of the car in which the dashboard is installed. By the way, the conventional method for matting such PVC resin vacuum molded products is as follows. That is, in this method, an inorganic fine powder such as powdered silica is applied and adhered to a PVC resin sheet before vacuum forming using an application section. However, such methods include
It comes with the following drawbacks: In other words, not only does the number of processing steps for the coating itself increase as described above, but when such a sheet is vacuum-formed, the stretching ratio differs depending on the part of the molded product, so the product may have an uneven degree of partial matting. So-called uneven gloss occurs. On the other hand, there is no known method for sufficiently achieving the purpose of matting by changing the formulation of a vinyl chloride resin composition (hereinafter referred to as a vinyl chloride resin composition). As a result of various studies on formulations that enable such matting, the present inventors have found that a special vinyl chloride resin can be used as the main vinyl chloride resin without adding any special processing steps after manufacturing the vinyl chloride resin sheet. The present invention was completed based on the knowledge that the above technical problems could be solved by using a copolymer. As is clear from the above description, the purpose of the present invention is to use a special formulation (use of a special copolymer and an appropriate amount of plasticizer) for the PVC resin composition, and then To provide a vacuum-formed product which is made into a sheet by the above method and which is sufficiently matte even when vacuum-formed and exhibits little matting during molding. Other purposes will become clear from the description below. The present invention is based on "vinyl chloride 99.0-99.
95% by weight and polyethylene glycol diacrylate or polyethylene glycol dimethacrylate having 4 to 50 polymerized units of ethylene glycol from 1.0 to
A composition consisting of 100 parts by weight of a vinyl chloride copolymer containing 0.05% by weight and 0 to 10 parts by weight of a plasticizer is vacuum-formed by calender molding or extrusion molding into a sheet. A vinyl chloride copolymer vacuum molded product.

'', and its structure and effects will be explained in detail below. Vinyl chloride copolymer used in the present invention: The copolymer is composed of 99.95% by weight or less of vinyl chloride monomer (hereinafter referred to as VCM) and a specific polyethylene glycol diacrylate or a specific polyethylene glycol diacrylate. It is a copolymer of polyethylene glycol dimethacrylate.

The pinyl chloride moiety in the copolymer is 99.0 to 99.9
Although the amount is 5% by weight, a portion thereof may be replaced with other vinyl monomers described below as long as the object of the present invention is not impaired. In that case, the amount of pinyl chloride in the vinyl chloride portion is at least 5% by weight, preferably at least 7% by weight, of the total polymer used, with the upper limit being the above-mentioned 99.95% by weight.
Next, the above-mentioned polyethylene glycol diacrylate (
Polyethylene glycol dimethacrylate (hereinafter referred to as PEGA) or polyethylene glycol dimethacrylate (hereinafter referred to as PEGM) refers to those in which the number n of repeating ethylene glycol groups in the polyethylene glycol moiety is 4 or 50, respectively, and is a combination of PEGA and PEGM. Alternatively, polyethylene glycol acrylate methacrylate, which is a corresponding mixed ester, can be polymerized with VCMR and used in the same manner. In PEGA or PEGM, if the number n of ethylene glycol group units is less than 4, the final matting effect of the molded product of the present invention will be insufficient, and if it exceeds 50, other physical properties, that is, blooming properties will be poor. Such a vacuum-formed product loses its practicality. The proportion of PEGA or PEGM in the copolymer used in the present invention is 1.0 to 0.
．． 05% by weight, and even if the ratio exceeds 1.0% by weight, the matting properties will not improve significantly. Furthermore, it is difficult to prepare such a high-ratio copolymer with no or very little unpolymerized PEGA or PEGM remaining in the copolymer by a conventional polymerization method. If the ratio is less than 0.05% by weight, the matte properties of the molded product of the present invention will be lost or significantly reduced. The method for producing the copolymer of VCMR and PEGA or PEGM (hereinafter referred to as the vinyl chloride copolymer for the present invention) used in the present invention follows a known method. That is, any of bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization may be used. However, unless there are other problems, suspension polymerization is preferable because it has good reproducibility of polymerization rate, degree of polymerization, etc., and it is easy to control the steps before and after polymerization. The degree of polymerization of the vinyl chloride copolymer for use in the present invention is not limited, but those of 400 to 1300 are preferably used. (b) Plasticizer used in the present invention; The blending mode of the PVC resin composition, which is the raw material for the sheet for producing the vacuum-formed product of the present invention, includes both hard, semi-rigid and soft modes, so it is used in the composition. The blending amount of the plasticizer can also be used in the range of 0 to 100 PHR (note: the weight percent of the additive to 10 parts by weight of the PVC resin or less).

The plasticizer used is not limited, but since the sheet extruded from the composition is vacuum formed, a slightly volatile plasticizer, a polyester plasticizer such as poly-1,3-butylene glycol adipate, and trimellitic acid can be used. Preferred are trimellitic acid plasticizers such as butyl and epoxy plasticizers such as epoxidized soybean oil. However, general plasticizers such as those described below can also be used alone or in combination with the polyester plasticizers. General plasticizers used in the raw material vinyl chloride resin composition include phthalic acid plasticizers such as dioctyl phthalate (DOP) and adipic acid plasticizers such as dioctyl phthalate (00A).
Even if the total amount of plasticizer used in the PVC resin composition for the present invention exceeds 100 PHR, there is no particular effect;
There are drawbacks such as a decrease in the strength of the extruded product. C. Other additives that can be added to the vinyl chloride resin composition for use in the present invention; examples of such additives in a broad sense include the following (1) to (2).

■ Other thermophilic resins include vinyl chloride polymers other than the vinyl chloride copolymer for the present invention, whose pinyl chloride content exceeds 5% by weight of the vinyl chloride portion in the vinyl chloride resin composition for the present invention. It can be used on the condition that it is not.

Other examples include A Shigeru resin, AS resin, M old S resin, chlorinated polyethylene, and urethane resin. The amount of these resins used is desirably equal to or less than the amount of the vinyl chloride copolymer for the present invention used in the composition. ■ The following rubbers can be used as other polymeric materials to be blended.

i.e. butadiene rubber, isof. Ren rubber, loprene rubber, isoptylene/gen rubber, or ethylene/propylene rubber.

The preferred usage amount is the same as in the case of (2) above.
Z■ Examples of the heat stabilizer to be mixed include the following agents. Namely, they are metal soaps such as Stear IJ lead stearate, cadmium stearate, barium stearate, zinc stearate, organotin stabilizers such as dibutyltin laurate, or Z or organic phosphite. The preferable amount of these heat stabilizers to be used is, for example, the amount required for the vinyl chloride polymer in the vinyl chloride resin composition for the present invention.
lOPHR is preferably 0.5 to same-day R. ■ The fillers to be mixed include the following organic and inorganic substances.

namely, wood flour, calcium carbonate, silica, talc, clay titanium oxide and carbon black. Although the amount used is not limited, it is preferably 5 to 50 PHR.

- Pigments to be blended include metal oxides such as zinc oxide, metal sulfides such as iron sulfide, sulfates such as lead sulfate, and various organic pigments such as quinacridone, phthalocyanine flue, or penzidine.

The amount used is preferably 1 to 1 OPHR. ■ Acrylic resin can be cited as a processing aid to be blended.

The amount used is preferably 2-20 PHR.

D. Method for mixing raw materials for the vinyl chloride resin composition for use in the present invention; any of the following mixers can be used according to a known method.

However, it is not limited to these. The mixing order and mixing conditions are also the same as in the known method. (e) Calendar molding or extrusion molding of the PVC resin composition for use in the present invention: According to a known method, the cross-wire conditions, calender molding conditions, or extrusion molding conditions are also the same as those of the known method.

By this molding, a sheet with a thickness of 0.2 to 2 bars is made. This sheet has a matte surface and a low gloss rate (the measurement method will be described later), for example, 30% or less. Vacuum forming of the sheet obtained in step E above: Either female molding or male molding can be used according to known methods.

The molding temperature is, for example, 180 to 200℃, 2-cho-tae to 2-cho.
It takes about a minute. (g) Unique effects of the vacuum-formed product of the present invention: It has a sufficient matting effect without adding any special process after producing the sheet described in (e) above or after vacuum forming the above-mentioned material.

Furthermore, when comparing the sheet and a product made by vacuum forming the sheet, the latter's optical selectivity is increased, that is, the matteness is extremely small. Therefore, the molded product of the present invention can be manufactured extremely efficiently as a necessary matte molded product, and there is little variation in the degree of matteness between multiple products as well as local unevenness within one product. The present invention will be explained below with reference to Examples. Example 1 1.0% by weight of PEGA n-14, VCM old 99
．． A monomer polymer containing 0.00% by weight was subjected to suspension polymerization at 5.0% to obtain a vinyl chloride copolymer having a degree of polymerization (hereinafter referred to as P) of 1300.

To this copolymer, 30 PHR of trimellitic acid ester (C-8, manufactured by Adeka Argus Co., Ltd.) as a plasticizer and 1 liter of epoxy oil (0113 fertilizer, manufactured by Adeka Argus Co., Ltd.)
Rudder HR, as other additives, calcium carbonate 20PHR
, ABS resin (Kanease B-17 manufactured by Kanebuchi Chemical Industry)
40PHR, barium zinc mixed heat stabilizer (N-726
Blood 2. Spotted HR, M-724 field 1. DBTL as a 4.0PHR antioxidant
I. Mark 1500 (Adeka Argus) as an OPHR chelator and carbon black 2.0 PHR were mixed as follows.

That is, put the above-mentioned raw materials into a ribbon blender,
The mixture was mixed 3 times while heating to 100°C to obtain a PVC resin composition for use in the present invention. Apply this composition to a 22◇ roll and
3000 for 20 minutes and further NBR (Hycarl0
42 manufactured by Nippon Zeon) and 20 PHR at the same temperature.
We trained the branch moat. This crane paste was passed through a 14,000mm 160 inverted L-shaped calender roll and then passed through a grain roll to obtain a 0.3-rib sheet. The surface gloss of the vacuum-formed product obtained by vacuum-forming the sheet thus obtained was compared with that of the molded product of Comparative Example 1. The results are shown in Table 1. Comparative Example 1 * The same procedure as in Example 1 was carried out except that a vinyl chloride homopolymer was used instead of a vinyl chloride copolymer.

The results are shown in Table 1. Table 1 Comparison of gloss before and after vacuum forming using calendar sheet K (Part 1)
) Note, *The visual judgment criteria and gloss rate measurement method are as follows.

※※Stripedness with the heating oven in which the sheet is placed before molding
Criteria for visual judgment: ◎, 0, △, ×, XX: Excellent, Good, Fair, Poor, Extremely poor, Excellent is glossy, Extremely poor is poor (no matting effect at all). Measuring method of gloss rate (%): Based on JIS Z-8741 method. ray angle 6
From the results in Table 1, the following is clear regarding Example 1 and Comparative Example 1. That is, even if a calender-formed sheet using a pinyl chloride homopolymer has an "excellent" matte state before vacuum forming, the matte state returns to "excellent" after the vacuum forming. On the other hand, the sheet using the copolymer of the present invention has no or very little reversion after vacuum forming compared to before vacuum forming, and is made of vinyl chloride resin vacuum matte using a simple manufacturing method. It turns out that it is useful as a molded product. Example 2 0.5% by weight of PEGA n-14, VCM old 9
A monomer mixture consisting of 9.50% by weight was subjected to suspension polymerization with 5 being 0 to obtain a vinyl chloride copolymer with P=1310.

To this copolymer, 30 PHR of trimellitic acid ester (C-8, manufactured by Adeka Argus Co., Ltd.) as a plasticizer, and lactic acid poxy oil (manufactured by 0113 Misaki Adeka Argus Co., Ltd.) were added.
OPHR, as other additives, calcium carbonate 2 cape HR
, A-spotted resin 40PHR, barium zinc mixed heat stabilizer (
M-726 plate 2. Spot HRM-724 Spot 1. (manufactured by HR Japan Interstap) 4. DBTL as HR antioxidant
Mark 1500 (manufactured by Adeka Argus) carbon black 2.0 was mixed as a chelator in the following manner.

That is, put the above-mentioned raw materials into a ribbon blender, and
The mixture was dug for 30 minutes while being heated to 000°C to obtain a vinyl chloride resin composition for use in the present invention. This composition is rolled and 13
The mixture was kneaded at 0° C. for 20 minutes, and 20 PHR of NBR was further added and kneaded at the same temperature for 20 minutes. This was made into a sheet and then cut into cubes with a cutter to create pellets.
The pellet thus obtained was passed through a 65-side extruder to a thickness of 0.
This sheet was molded into a three-rib sheet, and the surface gloss of the vacuum-formed product after vacuum-forming this sheet and this sheet was compared with that of the molded product of Comparative Example 2. The results are shown in Table 2. *Comparative Example 2 The same procedure as Example 2 was carried out except that a pinyl chloride homopolymer was used instead of the vinyl chloride copolymer.

The results are shown in Table 2. Table 2 Comparison of gloss before and after vacuum forming using extruded sheet Notes: *, *※; Each standard is the same as in Table 1. From the results in Table 2, the following is clear regarding Example 2 and Comparative Example 2. It is.

Claims (1)

[Claims] 1 Vinyl chloride copolymer consisting of 99.0 to 99.95% by weight of vinyl chloride and 1.0 to 0.05% by weight of polyethylene glycol diacrylate or polyethylene glycol dimethacrylate having 4 to 50 polymerized units of ethylene glycol Combined 100 parts by weight and plasticizer 0-10
A vacuum-formed vinyl chloride copolymer product obtained by vacuum-forming a sheet containing 0 parts by weight of a composition by calender molding or extrusion molding.