JPH04130149A - Vinyl chloride resin composition for composite glass-vinyl chloride resin molding, and composite glass-vinyl chloride resin molding prepared therefrom - Google Patents

Abstract

PURPOSE:To improve the flowability during injection molding and prepare a molding having a tack-free surface and excellent mechanical properties by compounding a vinyl chloride resin, a plasticizer, and a specific org. titanate compd. CONSTITUTION:The title compsn. is prepd. by compounding 100 pts.wt. vinyl chloride resin having an average degree of polymn. of 400-1500, 20-150 pts.wt. plasticizer (e.g. tri-2-ethylhexyl trimellitate), 1-15 pts.wt. org. titanate compd. of the formula (wherein R<1> is 1-8C alkyl; and R<2> is 4-30C alkyl) (e.g. isopropyltriisostearoyl titanate), and required amts. of a thermal stabilizer, a lubricant, a UV absorber, a flame retardant, a pigment, etc. The compsn. is injected to the peripheral part of a glass plate and molded with the plate to give the title composite molding.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a vinyl chloride resin composition for integral molding of glass and vinyl chloride resin used in vehicles, drugs, etc., and a glass and vinyl chloride resin composition using the same. This invention relates to an integrally molded resin body.

(Prior Art) Generally, rubber, vinyl chloride resin, etc. are used as frame materials (hereinafter referred to as moldings) used for window materials such as rear windows and quarter windows for automobiles.

Conventionally, these window materials have been attached to the vehicle body by fitting the glass into the frame of the vehicle body through a sealing material and then attaching a molding. However, the above-mentioned method is not economical because it is mainly manual work and involves a large number of steps.

In order to solve this problem, for example,
817, JP-A-62-68992, JP-A-2-6
The glass/vinyl chloride integral molding method (hereinafter referred to as the Mosier Wind method) described in Publication No. 0722, etc.
That is, a method is adopted in which a window material obtained by setting glass in a mold of an injection molding machine and integrally molding a frame material made of vinyl chloride resin around the periphery of the glass is attached to a vehicle body.

As the vinyl chloride resin used in the above module window system, a composition prepared by adding a plasticizer to a vinyl chloride homopolymer has been used. However, this composition has poor fluidity during injection molding, so it is necessary to increase the injection pressure, mold clamping pressure, etc. in order to completely cover the glass periphery with the injection molded product of vinyl chloride resin. However, there was a drawback that the glass was tightened with strong pressure and was easily damaged.

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 using a vinyl chloride resin with a low degree of polymerization improves fluidity. However, as the plasticizer retention performance decreases, the plasticizer bleeds out from inside the injection molded product, resulting in a decrease in the mechanical properties of the injection molded product and a tank-like appearance on the surface of the injection molded product. There was a drawback.

(Problems to be Solved by 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, which has excellent resin fluidity during injection molding. Another object of the present invention is to provide a glass/vinyl chloride resin integrally molded body having excellent mechanical properties and having no tank properties on the surface.

(Means for Solving the Problems) Any vinyl chloride resin may be used in the present invention, and in addition to vinyl chloride homopolymers,
A copolymer obtained by copolymerizing vinyl chloride with a polymerizable monomer other than vinyl chloride, a graft copolymer obtained by grafting vinyl chloride onto a polymer other than vinyl chloride, etc. can be used.

The above polymerizable monomer is not particularly limited as long as it has a reactive double bond, and examples include α-olefins such as ethylene, propylene, butylene, vinyl acetate, vinyl propionate, etc. vinyl esters,
Vinyl ethers such as butyl vinyl ether and cetyl vinyl ether, acrylic acid esters such as methyl acrylate and ethyl acrylate, methyl methacrylate,
Methacrylic acid esters such as ethyl methacrylate and phenyl methacrylate, aromatic vinyls such as styrene and α-methylstyrene, vinyl halides such as vinylidene chloride and vinyl fluoride, N-phenylmaleimide, N-
Examples include cyclohexylmaleimide and (7) N-IF converted mamaleimides. These may be used alone or in combination of two or more.

The polymer other than vinyl chloride is not particularly limited as long as it can be grafted with vinyl chloride, such as ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon oxide copolymer, etc. ethylene-ethyl acrylate copolymer, ethylene-ethyl acrylate-carbon oxide copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer,
Examples include acrylonitrile-butadiene copolymer, polyurethane, chlorinated polyethylene, and chlorinated polypropylene. These may be used alone or in combination of two or more.

The composition of the above copolymer is as described above, but if the content of structural units other than vinyl chloride in the copolymer increases, the mechanical properties of the final molded product will deteriorate, so the content should be 40% by weight or less. preferable.

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 have tackiness.
If it becomes too large, the fluidity of the vinyl chloride resin composition during injection molding will decrease, so 400 to 1500 is preferable.

Any method may be used to produce the above-mentioned vinyl chloride resin. For example, the known suspension polymerization method, emulsion polymerization method, and solution polymerization method, which are usually carried out in the polymerization of vinyl chloride using a radical polymerization initiator, may be adopted. Legal method, bulk polymerization method, etc. are mentioned. 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 vinyl chloride resin, and examples include dimethyl phthalate, diethyl phthalate, di-n-octyl phthalate, Phthalic acids such as diisodecyl phthalate, dibutyl adipate, di-n adipate
- Adipic acids such as hexyl, phosphoric acids such as tributyl phosphate, tri-2-ethylhexyl phosphate, trimeline)
[-MJ-Diisodecyl phthalate (hereinafter referred to as DIDP), which includes trimellitic acid-based products such as 2-ethylhexyl and tributyl trimellitate, chlorinated paraffin-based products, and polyester-based products, has low volatility and excellent fogging resistance. , tri-2-ethylhexyl trimellitate (hereinafter referred to as TOTM) is preferably used. These may be used alone or in combination of two or more.

If the content of the plasticizer in the vinyl chloride resin composition is low, the fluidity during injection molding will decrease, and if it is high, tank properties will appear on the surface of the final molded product. 20-150 per 100 parts by weight
Parts by weight.

The organic titanate compound used in the present invention is the following (I)
It is a compound represented by the formula.

11...(I)R'-0-Ti
(〇-C-R2)3 In the formula, R1 and R2 represent an alkyl group, and as the number of carbon atoms in R increases, the compatibility with the vinyl chloride resin deteriorates, and the mechanical properties of the final molded product decreases, so 1
~8, and when the number of carbon atoms in R2 decreases, the fluidity of the vinyl chloride resin composition during injection molding decreases, resulting in poor moldability, and when it increases, the compatibility with the vinyl chloride resin deteriorates, resulting in a final It is 4 to 30 because the mechanical properties of the molded product obtained are lowered.

Examples of the organic titanate compounds include hexyltricapryl titanate, ethyl trilauryl titanate, isopropyl trilauryl titanate, ethyl triisostearoyl titanate, isopropyl triisostearoyl titanate, n-octyl triisostearoyl titanate, and 2-ethylhexyl. Examples include triisostearoyl titafoot, butyl trihhenyl titanate, and the like. These may be used alone or in combination of two or more.

If the content of the above-mentioned organic titanate compound in the vinyl chloride-based resin composition decreases, the fluidity during injection molding will decrease, and if the content increases, the mechanical properties of the final molded product will decrease. The amount is 1 to 15 parts by weight per 100 parts by weight of the resin.

The vinyl chloride resin composition of the present invention may include, if necessary,
Tin-based stabilizers such as butyltin malate and octyltin malate, organometallic salt-based stabilizers such as calcium stearate, barium stearate, and zinc stearate, metal soap-based stabilizers, epoxidized soybean oil, epoxidized linseed oil, etc. Heat stabilizers such as organic epoxy compound stabilizers, aliphatic hydrocarbon lubricants such as polyethylene wax and paraffin wax, higher aliphatic alcohol lubricants such as stearyl alcohol, and higher fatty acid lubricants such as stearic acid and hydroxystearic acid. , fatty acid amide-based lubricants, fatty acid ester-based lubricants, hensifenone-based ultraviolet absorbers,
Ultraviolet absorbers such as hensitriazole ultraviolet absorbers, acrylic processing aids, flame retardants such as halogen flame retardants, phosphorus flame retardants, fillers such as calcium carbonate, clay, mica, titanium oxide, carbon black, etc. Pigments and the like may also be added.

Although any method may be adopted for producing the glass/vinyl chloride resin integrally molded body, injection molding is preferable. A vinyl resin composition is injection molded and integrally formed around the periphery of the glass.

The above-mentioned glass is not particularly limited, and includes, for example, tempered glass for automobiles, tempered glass such as laminated glass for automobiles, untempered 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, a known glass/vinyl chloride resin composition such as an epoxy resin adhesive, a phenol-modified epoxy resin adhesive, or a polyamide resin adhesive is applied to the glass surface that comes into contact with the vinyl chloride resin composition at the glass periphery. The vinyl chloride resin composition may be injection molded after a layer of adhesive 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. , screw-in-line method, etc., and a 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 plunger type injection molding, the pressure inside the cylinder of the injection molding machine is preferably 100 to 300 kg/Cl+, and the vinyl chloride resin composition in the cylinder of the injection molding machine is heated at 160 to 200°C. It is preferable to bring the material into a molten state and fill 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 the glass/vinyl chloride resin integrally molded article of the second invention.

In FIG. 1, 3 is a mold consisting of an upper mold 31 and a lower mold 32, and the mold 3 has a resin injection port 34 for injecting a molten vinyl chloride resin composition 21, and a cooling water for cooling the mold. A vibrator 33 is installed.

35 is a cavity formed by the upper mold 31 and the lower mold 32, and is formed from a central cavity 37 that sandwiches the glass 1 and a peripheral cavity 36 that is filled with the molten vinyl chloride resin composition 21. ing.

The manufacturing method will be explained below.

First, as shown in FIG. 1(A), the glass 1 is placed in the central cavity 37, and the mold is closed. Next, as shown in FIG. 1(b), after the mold 3 is clamped, the molten vinyl chloride resin composition 21 is poured into the peripheral cavity 36 through the resin injection port 34.
When the molten vinyl chloride resin composition 21 is injected into the cavity 35 and the mold 3 is cooled by flowing cooling water through the cooling water vibrator 33, as shown in FIG. The molten vinyl chloride resin composition 21 injected into the peripheral gap 36 is cooled and solidified, and the vinyl chloride resin molded body 2 is integrally formed on the peripheral edge of the glass 10. Next, as shown in FIG. ), when the mold 3 is opened and taken out, a glass/vinyl chloride resin integral molded body A is formed, in which the glass l and the vinyl chloride resin molded body 2 are integrally injection molded.
is obtained.

(Example) The present invention will be explained in detail below.

Note that "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 regarding vinyl chloride resin composition (I) Fluidity The obtained vinyl chloride resin composition was supplied to a Koka type flow tester (manufactured by Shimadzu Corporation, model: CFT-500) and heated at 170°C11. The measurement was carried out using a 1φ×10++a nozzle under a load of OOkgf/cffl.

(2) 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, and J
Measured according to IS K6745.

(Press molding conditions) Preheating: 170'C, 23 minutes Pressing: 50 kg/C1M, 4 minutes Cooling: 10 minutes (3) Tackiness Thickness produced by press molding the obtained vinyl chloride resin composition under the above conditions 7 2mm vinyl chloride resin plates
After being left in an atmosphere of 0° C. and 195% RH for one week, the surface condition was subjected to a sensory test in an atmosphere of 22° C. and 165% RH, and the tank properties were evaluated according to the following criteria.

○: No tank property ×: The sample surface is in a stale state, and there is tank property. A vinyl chloride resin with a thickness of 2 mm was prepared by press-molding the vinyl chloride resin composition obtained with Shore hardness under the above conditions. Using a board, measure the hardness of its surface using a Shore hardness tester (manufactured by Ueshima Seisakusho,
Model: HD-103N).

2. Physical properties of the glass/vinyl chloride resin integral molded product (I) Shot shot resistance The obtained glass/vinyl chloride resin integral molded product was visually observed, and the shot shot resistance was evaluated according to the following criteria. evaluated.

○: The molded object of the vinyl chloride resin composition at the periphery of the glass is present without any missing pieces. 2) The glass/vinyl chloride resin integrally molded body that has obtained tackiness is held at 70°.
After being left in an atmosphere of C195%RH for one week, the surface condition of the molded product of the vinyl chloride resin composition was changed to 22°C165.
A sensory test was conducted in an atmosphere of %RH to evaluate the tank properties according to the following criteria.

○: No tank property ×: The sample surface is in a stale state, with tack property 1-4 1-4 Predetermined amounts of vinyl chloride resin, plasticizer, organic titanate compound, and barium zinc compound shown in Table 1 Liquid stabilizer (manufactured by Adeka Argus, trade name, AC, 190) 1.5
0.5 parts of barium-zinc powder stabilizer (manufactured by Adeka Argus Co., Ltd., trade name: AP550) and organic epoxy compound stabilizer (manufactured by Adeka Argus Co., Ltd., trade name: 0-13
0P) 3.0 parts in a super mixer (manufactured by Kawada Seisakusho Co., Ltd.)
After stirring for 20 minutes while raising the temperature to 100°C, the contents were transferred to a cooling mixer (manufactured by Kawada Seisakusho Co., Ltd., model: C0-100),
The mixture was stirred for 15 minutes and cooled to below 30°C to obtain a compound.

The obtained compound was supplied to an extruder (model SLM-50, manufactured by Choen Seisakusho Co., Ltd.) whose mold temperature and barrel tip temperature were set at 155°C, and was melt-kneaded to obtain an extrudate.

After cooling the obtained extrudate, a cold cant pelletizer (manufactured by Union Plastics, model: UC-15) was used.
2) and cut to obtain a pellet-shaped vinyl chloride resin composition.

Using the obtained vinyl chloride resin composition, various physical properties regarding the vinyl chloride resin composition were measured based on the measurement method described above, and the results are shown in Table 1.

Next, an injection and molding machine (manufactured by Toshiba Machine Co., Ltd., model: 1S-3) was used.
50E), an epoxy resin adhesive (manufactured by Cemedine Co., Ltd., product name: Cemedine 150) was applied to the periphery of the mold.
0) Glass layer formed with a width of 1 mark and a thickness of 25 μm (30
After arranging and clamping the mold, the pellet-shaped vinyl chloride resin composition was supplied to the injection molding machine, and the vinyl chloride resin composition was heated to 190°C. The molten vinyl chloride resin composition was injected from the resin injection port at an internal pressure of 170 kg/ci 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. A resin integrally molded body was obtained.

Using the obtained glass/vinyl chloride resin integral molded body, various physical properties of 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.

(The following is a blank space) (Effects of the invention) The composition of the vinyl chloride resin composition of the present invention is as described above, and includes a vinyl chloride resin, a specific amount of a plasticizer, and a specific amount of a specific amount of the formula (I). Since it contains an organic titanate compound, it has excellent fluidity during injection molding, and the surface of a molded product produced using the vinyl chloride resin composition has no tank properties and has excellent surface hardness.

In the glass/vinyl chloride resin integrally molded article of the second invention, the vinyl chloride resin composition is injection molded on the peripheral edge of the glass, so that the vinyl chloride resin composition has excellent fluidity during injection molding. The vinyl chloride resin composition completely wraps around the glass periphery without increasing the injection pressure, mold clamping pressure, etc., preventing a short shot condition, and the molded product of the vinyl chloride resin composition at the glass periphery. It is possible to obtain a glass/vinyl chloride resin integral molded article with no chipping, and the surface of the vinyl chloride resin molded article of the obtained glass/vinyl chloride resin integral molded article does not exhibit tackiness.

[Brief explanation of drawings]

Figure 1 (a), (b), (c) and (d) are the invention 2
FIG. 2 is a schematic cross-sectional view illustrating a process of injection molding and manufacturing a glass/vinyl chloride resin integrally molded body. A-glass/vinyl chloride resin integral molding, 1-glass, 2- vinyl chloride resin molding, 3- mold.

Claims (1)

[Claims] 1. 100 parts by weight of vinyl chloride resin and 20 to 15 parts by weight of plasticizer
1. A vinyl chloride resin composition for integral molding of glass and vinyl chloride resin, comprising 0 parts by weight and 1 to 15 parts by weight of an organic titanate compound represented by formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R^1 is an alkyl group with 1 to 8 carbon atoms, R^2 is an alkyl group with 4 to 30 carbon atoms) 2. Patent A glass/vinyl chloride resin integral molded article, 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.