JPH04224919A - Vinyl chloride resin composition for integral molding of glass and vinyl chloride resin, and integral molded body of glass and vinyl chloride resin using the composition - Google Patents

Abstract

PURPOSE:To manufacture a vinyl chloride resin composition of superior fluidity at the time of injection molding for vinyl chloride resin integral molding by blending the specified volume of a plasticizer and the specified volume of trialcohol with vinyl chloride resin. CONSTITUTION:A glass and vinyl chloride resin integral molded body is composed of 100 pts.wt. of vinyl chloride, 20-150 pts.wt. of a plasticizer and 0.5-15 pts.wt. of trialcohol represented by the formula (1) (representing n=0-30). As for vinyl chloride resin, in addition to a simple copolymer of vinyl chloride, a copolymer of the same, a graft copolymer or the like is used. As for the plasticizer, any material to be compatible with vinyl chloride resin can be used without any particular restrictions. Di-isodecyl phthalate or tri-2-ethyhexyl trimellitate is used suitably. As trialcohol, for example, trirnetylolpropane or the like is used. The vinyl chloride resin composition is injection molded and formed integrally on the periphery of glass.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition for integral molding of glass and vinyl chloride resin for use in vehicles, buildings, etc., and to an integral glass and vinyl chloride resin molded article using the composition.

0002

2. Description of the Related Art Generally, rubber, vinyl chloride resin, etc. are used as frame materials (hereinafter referred to as moldings) for window materials such as rear windows and quarter windows for automobiles. Conventionally, these window materials were attached to the car body by fitting the glass into the frame of the car body through a sealing material and then attaching a molding, but this method mainly required manual labor. However, it was not economical due to the large number of steps involved.

[0003] In order to solve the above problem, various methods have been proposed. For example, Japanese Patent Laid-Open No. 62-68992, Japanese Patent Laid-Open No. 2-60722, etc. disclose a method of integrally molding glass and vinyl chloride resin. (hereinafter referred to as the modular window method), that is, the glass is set in the mold of an injection molding machine, a frame material made of vinyl chloride resin is integrally molded around the glass periphery, and the resulting window material is attached to the vehicle body. A method has been proposed.

As the vinyl chloride resin used in the above-mentioned module window system, a composition in which a plasticizer is added to a vinyl chloride homopolymer is used. however,
This composition has poor fluidity during injection molding, so it is necessary to increase the injection pressure, mold clamping pressure, etc. to completely cover the peripheral edge of the glass with the injection molded product of vinyl chloride resin. The disadvantage is that the glass is easily damaged because it is tightened with strong pressure.

On the other hand, as a method to improve the fluidity of vinyl chloride resin during injection molding, attempts have been made to lower the degree of polymerization of vinyl chloride resin, but when using a vinyl chloride resin with a low degree of polymerization, the fluidity Although the plasticizer retention performance is improved, the plasticizer bleeds out from inside the obtained injection molded product, resulting in a decrease in the mechanical properties of the injection molded product and the tackiness of the surface of the injection molded product. It had the disadvantage of being frightening.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above drawbacks, and provides a vinyl chloride resin composition for integral molding of glass and vinyl chloride resin with excellent fluidity during injection molding, and mechanical properties. The purpose of the present invention is to provide a glass/vinyl chloride resin integrally molded body which has excellent properties and has no tackiness on the surface.

[0007]

[Means for Solving the Problems] The vinyl chloride resin used in the present invention includes not only a homopolymer of vinyl chloride but also a copolymer of vinyl chloride and a polymerizable monomer copolymerizable with vinyl chloride. Examples include polymers and graft copolymers obtained by graft-polymerizing vinyl chloride onto polymers. The above polymerizable monomer is not particularly limited as long as it can be copolymerized with vinyl chloride, and examples thereof include α-olefins such as ethylene, propylene, butylene, vinyl acetate, vinyl propionate, etc. Vinyl esters, vinyl ethers such as butyl vinyl ether, cetyl vinyl ether,
Acrylic acid esters such as methyl acrylate and ethyl acrylate; methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, and phenyl methacrylate; aromatic vinyls such as styrene and α-methylstyrene; , vinyl halides such as vinylidene chloride and vinyl fluoride, and N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide. These may be used alone or in combination of two or more.

The above polymer is not particularly limited as long as it can graft-polymerize vinyl chloride; for example, ethylene-vinyl acetate copolymer,
Ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-ethyl acrylate copolymer, ethylene-ethyl acrylate-carbon monoxide copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer Union,
Examples include acrylonitrile-butadiene copolymer, polyurethane, chlorinated polyethylene, and chlorinated polypropylene. These may be used alone or in combination of two or more.

[0009] The above-mentioned copolymer is preferably 40% by weight or less because if the content of structural units other than vinyl chloride in the copolymer increases, the mechanical properties of the final molded product will deteriorate. In addition, if the average degree of polymerization of the vinyl chloride resin becomes small, the mechanical properties of the final molded product will decrease, and the holding power of the plasticizer will decrease, causing the surface of the molded product to become tacky. If this happens, the fluidity of the vinyl chloride resin composition during injection molding will decrease, so the
00 is preferred.

[0010] Any method may be adopted for producing the above-mentioned vinyl chloride resin, for example, the known suspension polymerization method or emulsion polymerization method which is commonly carried out in the polymerization of vinyl chloride using a radical polymerization initiator. , solution polymerization method, bulk polymerization method, etc. The suspension polymerization method is preferably employed because the obtained polymer is unlikely to contain impurities and the manufacturing cost is relatively low.

The plasticizer used in the present invention is not particularly limited as long as it is compatible with the above-mentioned vinyl chloride resin. For example, dimethyl phthalate, diethyl phthalate, di-n phthalate, etc. - Phthalic acids such as octyl and diisodecyl phthalate, adipic acids such as dibutyl adipate and di-n-hexyl adipate, phosphoric acids such as tributyl phosphate and tri-2-ethylhexyl phosphate, trimellitic acid - Examples include trimellitic acid types such as tri-2-ethylhexyl and tributyl trimellitate, chlorinated paraffin types, and polyester types. Tri-2-ethylhexyl mellitic acid (hereinafter referred to as TOTM) is preferably used. These may be used alone or in combination of two or more.

[0012] If the amount of the plasticizer added is small, the fluidity during injection molding will decrease, and if it is too large, tackiness will appear on the surface of the final molded product. The amount is 20 to 150 parts by weight. The trial alcohol used in the present invention is represented by general formula [I].

[0013]

[Case 2]

In the formula, n is limited to 0 to 30 because as it becomes large, the compatibility with the vinyl chloride resin decreases and the mechanical properties of the obtained molded product decrease. Examples of the trial alcohol include trimethylolpropane, trimethylolpropane, trimethylolbutane, trimethylol octane, trimethylol dodecane, trimethylol heptadecane, trimethylol docosane, and trimethylol triacontane.

[0015] The above trial alcohols may be used alone or in combination of two or more, and the amount added is as follows:
If the amount is too low, the fluidity of the vinyl chloride resin composition during injection molding will be reduced, and if it is too large, the mechanical properties of the final molded product will be reduced. ~15 parts by weight. The vinyl chloride resin composition of the present invention may optionally contain tin stabilizers such as butyltin maleate and octyltin maleate, and organic metal salts such as calcium stearate, barium stearate, and zinc stearate. Heat stabilizers such as metal soap stabilizers, organic epoxy compound stabilizers such as epoxidized soybean oil and epoxidized linseed oil, polyethylene wax,
Aliphatic hydrocarbon lubricants such as paraffin wax, higher aliphatic alcohol lubricants such as stearyl alcohol, higher fatty acid lubricants such as stearic acid and hydroxystearic acid, fatty acid amide lubricants, fatty acid ester lubricants, etc. Lubricants, UV absorbers such as benzophenone UV absorbers and benzotriazole UV absorbers, acrylic processing aids, halogen flame retardants, phosphorus flame retardants and other flame retardants, calcium carbonate, clay, mica, etc. Fillers, titanium oxide, pigments such as carbon black, etc. may be added.

[0016] Although any method may be adopted for producing the glass/vinyl chloride resin integrally molded article, it is preferable to use injection molding. , the vinyl chloride resin composition is injection molded and integrally formed on the peripheral edge of the glass. The above-mentioned glass is not particularly limited, and includes, for example, processed glass such as tempered glass for automobiles, laminated glass for automobiles, unprocessed glass for architectural use, and the like. These glasses are placed in a mold, and the vinyl chloride resin composition is injection molded onto the periphery of the mold and integrated. Then, apply a known glass/vinyl chloride resin such as an epoxy resin adhesive, a phenol-modified epoxy resin adhesive, or a polyamide resin adhesive to the glass surface that comes into contact with the vinyl chloride resin composition at the periphery of the glass. The vinyl chloride resin composition may be injection molded after a layer of adhesive for adhering the composition is provided in advance.

The injection molding method is not particularly limited as long as it can be injection molded without thermally decomposing the vinyl chloride resin composition. For example, plunger method, plunger pre-plastic method, screw method, etc. - Pre-plastic method, screw-in-line method, etc. are listed, and the plunger method is preferably used. The plunger injection molding is a molding method in which the vinyl chloride resin composition is heated and fluidized in a heated cylinder, and then pushed into a mold by an extrusion ram with a plunger.

In the above-mentioned plunger type injection molding, the pressure inside the cylinder of the injection molding machine is 100 to 300 kg.
/cm2, and it is preferable that the vinyl chloride resin composition in the cylinder of the injection molding machine be molten at 160 to 200°C, and then filled into the cavity of the mold. Hereinafter, with reference to the drawings, a process of injection molding a vinyl chloride resin composition to integrally form a molded body on the peripheral edge of the glass will be described.

FIG. 1 is a schematic cross-sectional view illustrating the process of injection molding and manufacturing a glass/vinyl chloride resin integrally molded article according to the second invention. In FIG. 1, 3 is an upper mold 31 and a lower mold 3
The mold 3 is provided with a resin injection port 34 for injecting the molten vinyl chloride resin composition 21 and a cooling water pipe 33 for cooling the mold. 35 is upper mold 3
1 and a lower mold 32, the cavity is formed of a central cavity 37 that holds the glass 1 therebetween and a peripheral cavity 36 that is filled with the molten vinyl chloride resin composition 21.

The manufacturing method will be explained below. First, Figure 1 (
As shown in a), the glass 1 is placed in the central cavity 37 and the mold is closed. Next, as shown in Figure 1 (b), the mold 3
After the mold is clamped, the molten vinyl chloride resin composition 21 is injected into the peripheral cavity 36 from the resin injection port 34, and the molten vinyl chloride resin composition 21 is poured into the cavity 35.
When cooling water is poured into the cooling water pipe 33 to cool the mold 3, as shown in FIG.
The molten vinyl chloride resin composition 21 injected into the glass 1 is cooled and solidified, and the vinyl chloride resin molded body 2 is integrally formed on the periphery of the glass 1 . Next, as shown in FIG. 1(d), when the mold 3 is opened and taken out, a glass/vinyl chloride resin integral molded body A, in which the glass 1 and the vinyl chloride resin molded body 2 are integrally injection molded, is obtained. can get.

[0021]

[Examples] Examples of the present invention will be described below. In addition,"
"Parts" means "parts by weight." The methods for measuring the physical properties of the vinyl chloride resin composition and glass/vinyl chloride resin integral molded article shown in the results are as follows. 1. Physical properties of vinyl chloride resin composition ■Fluidity The obtained vinyl chloride resin composition was fed to a Koka type flow tester (manufactured by Shimadzu Corporation, model: CFT-500) and tested at 170°C and 100 kgf/cm2. 1 under load conditions
Measurement was performed using a nozzle of φ×10 mm.

■ Tensile strength The obtained vinyl chloride resin composition was press-molded under the following conditions to produce a vinyl chloride resin plate with a thickness of 2 mm.
Measured in accordance with SK6745. (Press forming conditions) Preheating: 170℃, 3 minutes; Press: 50kg/cm2
, 4 minutes; Cooling: 10 minutes ■Tackiness A vinyl chloride resin plate with a thickness of 2 mm produced by press-molding the obtained vinyl chloride resin composition under the above conditions was
After being left in an atmosphere of 95% RH at 22° C. for one week, the surface condition was subjected to a sensory test at 22° C. and 65% RH, and the tackiness was evaluated according to the following criteria.

○: No tackiness ×: Sample surface is sticky, tackiness ■
Shore hardness Using a 2 mm thick vinyl chloride resin plate prepared by press-molding the obtained vinyl chloride resin composition under the above conditions, the surface hardness was measured using a Shore hardness meter (manufactured by Uejima Seisakusho, model: HD). -103N). 2. Physical properties of glass/vinyl chloride resin integrally molded body ■ Short shot resistance The resulting glass/vinyl chloride resin integral molded body was visually observed and its short shot resistance was evaluated according to the following criteria. .

○: The molded object of the vinyl chloride resin composition at the periphery of the glass is present without missing. ×: The molded object of the vinyl chloride resin composition at the periphery of the glass is partially missing and shorted. The glass/vinyl chloride resin integrally molded body that exists in the shot state has tack properties and is heated to 70°C.
After being left in an atmosphere of 95% RH for one week, the surface condition of the molded product of the vinyl chloride resin composition was evaluated at 22°C and 65% RH.
A sensory test was conducted in an atmosphere of H and the tackiness was evaluated according to the following criteria.

○: No tackiness ×: The sample surface was sticky, with tackiness Examples 1 to 6, Comparative Examples 1 to 5 The predetermined amounts of vinyl chloride resin, plasticizer, and trialcohol shown in Table 1 were used. -Al and barium-zinc liquid stabilizers (Adekar)
1.5 parts of barium-zinc powder stabilizer (manufactured by Adeka Air Gas Co., Ltd., trade name; AC-190);
AP-550) 0.5 part and an organic epoxy compound stabilizer (manufactured by Adeka Argas Co., Ltd., trade name: O-130P)3.
0 parts to a super mixer (manufactured by Kawada Seisakusho Co., Ltd., model: SM
G-100) and heated to 100℃ for 20 minutes.
After stirring for a minute, the contents were transferred to a cooling mixer (manufactured by Kawada Seisakusho Co., Ltd., model: CO-100), stirred for 15 minutes, and cooled to below 30°C to obtain a compound.

The obtained compound was supplied to an extruder (manufactured by Nagata Seisakusho Co., Ltd., model: SLM-50) whose mold temperature and barrel tip temperature were set at 155° C., and was melt-kneaded to obtain an extrudate. After the obtained extrudate was cooled, it was fed to a cold cut pelletizer (manufactured by Union Plastics, model: UC-152) and cut to obtain a vinyl chloride resin composition in the form of pellets.

Using the obtained vinyl chloride resin composition, various physical properties of the vinyl chloride resin composition were measured based on the measurement method described above, and the results are shown in Table 1. Next, a layer of epoxy resin adhesive (manufactured by Cemedine Co., Ltd., trade name: Cemedine 1500) was applied to the periphery of the mold in a mold installed in an injection molding machine (manufactured by Toshiba Machine Co., Ltd., model: IS-350E) with a width of 1 cm.
m, glass formed to a thickness of 25 μm (300 x 300 x
After arranging and clamping the mold, the pelletized vinyl chloride resin composition was fed to the injection molding machine, and the vinyl chloride resin composition was heated to 190°C. After melting, the pressure inside the cylinder from the resin injection port is 17
The molten vinyl chloride resin composition was injected at a rate of 0 kg/cm2 into the cavity.

Next, the mold is cooled by flowing cooling water through the cooling water pipe for mold cooling, and the molten vinyl chloride resin composition in the cavity is cooled and solidified, and then the mold is opened and taken out. - An integrally molded vinyl chloride resin body was obtained. Using the obtained glass/vinyl chloride resin integral molded body, various physical properties regarding the glass/vinyl chloride resin integral molded body were measured based on the measurement method described above, and the results are shown in Table 1.

[0029]

[Table 1]

[0030]

Effects of the Invention The composition of the vinyl chloride resin composition of the present invention is as described above, and since a specific amount of plasticizer and a specific amount of trial alcohol are blended with the vinyl chloride resin, injection It has excellent fluidity during molding, and the surface of a molded product produced using the vinyl chloride resin composition has no tackiness and has excellent surface hardness.

[0031] In the glass/vinyl chloride resin integrally molded article of the present invention 2, since the vinyl chloride resin composition is injection molded on the peripheral edge of the glass, the vinyl chloride resin composition is superior during injection molding. The vinyl chloride resin composition exhibits fluidity, and the vinyl chloride resin composition completely wraps around the glass periphery without increasing the injection pressure, mold clamping pressure, etc., and does not cause a short shot state. It is possible to obtain a glass/vinyl chloride resin integrally molded body with no missing parts, and the surface of the vinyl chloride resin molded body of the obtained glass/vinyl chloride resin integrally molded body does not exhibit tackiness. .

[Brief explanation of the drawing]

[Fig. 1] Fig. 1 (a), (b), (c), and (d) are schematic cross-sectional views illustrating the process of injection molding and manufacturing the glass/vinyl chloride resin integrally molded article of the present invention 2. be.

[Explanation of symbols]

A Glass/vinyl chloride resin integrally molded body 1
Glass 2 PVC resin molded body 3 Mold

Claims (2)

[Claims] Claim 1: 100 parts by weight of vinyl chloride resin, 2 parts by weight of plasticizer
A vinyl chloride resin composition for integral molding of glass and vinyl chloride resin, comprising 0 to 150 parts by weight and 0.5 to 15 parts by weight of a trial alcohol represented by the general formula [I]. [Chemical formula 1] (In the formula, n=0 to 30.) 2. A glass/vinyl chloride resin integral molding characterized in that the vinyl chloride resin composition according to claim 1 is injection molded and integrally formed on the peripheral edge of the glass. body.