JPH04272951A - Vinyl chloride resin composition for integral glass/vinyl chloride resin molding and integral glass/vinyl chloride resin molding prepared by using same - Google Patents

Abstract

PURPOSE:To provide the title composition having improved injection moldability and can give a molding having a tackfree surface and improved surface hardness by mixing a vinyl chloride resin with a plasticizer, specified di- and/or tri- carboxylic acids or a fatty acid aryl ester. CONSTITUTION:100 pts.wt. vinyl chloride resin of an average degree of polymerization of 400-1500 is mixed with 2-150 pts.wt. plasticizer and 0.5-10 pts.wt. dicarboxylic acid of formula I (wherein n is 2-34) and/or tricarboxylic acid of formula II (wherein m is 0-32) or fatty acid aryl ester of formula III (wherein R<1> is 5-30 C alkyl; and R<2> is phenyl, alpha-naphthyl or beta-naphthyl) to obtain a vinyl chloride resin composition for an integral glass/vinyl chloride molding. This composition is poured into the cavity of a mold containing glass at the center of the cavity and solidified by cooling to obtain an integral glass/vinyl chloride resin molding.

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-butyl 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 above-mentioned 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 dicarboxylic acid used in the present invention is represented by general formula (1).

[0013]

[C4]

[0014] In the formula, when n becomes small, the melting point becomes high and the vinyl chloride resin does not melt when molded, and when n becomes large, the compatibility with the vinyl chloride resin decreases, and the mechanical properties of the molded product decrease. Therefore, it is limited to 2 to 34. Examples of the dicarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, eicosanedioic acid, triacontanedioic acid, hexatriacontanedioic acid, and the like.

The tricarboxylic acid used in the present invention is represented by the general formula (2).

[0016]

[C5]

In the formula, n is limited to 0 to 32 because as it becomes large, the compatibility with the vinyl chloride resin decreases and the mechanical properties of the molded product decrease. As the above tricarboxylic acid,
For example, 1,2,3-propanetricarboxylic acid, 1,3
, 5-pentanetricarboxylic acid, 1,8,15-pentadecanetricarboxylic acid, 1,12,23-tricosanetricarboxylic acid, tritetracontanetricarboxylic acid, 1
, 34,67-heptahexacontantricarboxylic acid and the like.

The above dicarboxylic acid and tricarboxylic acid are
They may be used alone or in combination of two or more, and if the amount added is small, the fluidity of the vinyl chloride resin composition during injection molding will decrease, and if it is too large, the final molding will be affected. Since the mechanical properties of the body deteriorate, the amount is 0.5 to 10 parts by weight per 100 parts by weight of the vinyl chloride resin.

[0019] In the invention according to claim 2, a fatty acid aryl ester represented by the general formula (3) is used in place of the above carboxylic acid.

[0020]

[C6]

In the formula, R1 is an alkyl group, and if the number of carbon atoms becomes small, it will evaporate during molding, and if it becomes large, the compatibility with vinyl chloride resin will decrease, and the mechanical properties of the obtained molded product will deteriorate. decreases, the number of carbon atoms is limited to 5 to 30, and R2 is a phenyl group, α-naphthyl group, or β
- indicates a naphthyl group. If R2 has three or more aromatic rings, for example, an anthracenyl group, the melting point of the fatty acid aryl ester will be high and will not melt during molding, so it is not used in the present invention.

Examples of the fatty acid aryl esters include phenyl caproate, phenyl laurate, α-naphthyl laurate, β-naphthyl laurate, phenyl myristate, α-naphthyl myristate, phenyl stearate, and stearin. Examples thereof include α-naphthyl acid, β-naphthyl stearate, phenyl behenate, α-naphthyl behenate, phenyl montanate, and phenyl melisinate.

[0023] The above fatty acid aryl esters may be used alone or in combination of two or more, and if the amount added is small, the fluidity of the vinyl chloride resin composition during injection molding will decrease. If the amount increases, the mechanical properties of the final molded product will deteriorate, so the amount is 0.5 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin. 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 organic epoxy compound stabilizers such as metal soap stabilizers, epoxidized soybean oil and epoxidized linseed oil, aliphatic hydrocarbon lubricants such as polyethylene wax and paraffin wax, and stearyl alcohol. lubricants such as higher aliphatic alcohol-based lubricants such as stearic acid and hydroxystearic acid, fatty acid amide-based lubricants, and fatty acid ester-based lubricants, benzophenone-based ultraviolet absorbers, and benzotriazole-based ultraviolet rays. UV absorbers such as absorbers, acrylic processing aids, flame retardants such as halogen flame retardants and phosphorus flame retardants, fillers such as calcium carbonate, clay, and mica, pigments such as titanium oxide and carbon black. etc. may be added.

[0024] Although any method may be adopted for producing the glass/vinyl chloride resin integrally molded body, injection molding is preferably used. The vinyl chloride resin composition according to claim 1 or 2 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
It is placed in a mold, and the vinyl chloride resin composition is injection molded on the periphery of the mold and integrated. In order to further improve the adhesiveness between the glass and the vinyl chloride resin composition,
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 periphery of the glass. 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, and examples include the plunger method, plunger pre-plastic method, and screw molding method. - 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 manufacturing a glass/vinyl chloride resin integrally molded article according to claim 3 by injection molding. 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 a cavity formed by the upper mold 31 and the lower mold 32;
A central gap 37 that sandwiches the glass 1 and a peripheral gap 36 that is filled with the molten vinyl chloride resin composition 21.
It is formed from.

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.

[0029]

[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 pelletized using a Koka flow tester (manufactured by Shimadzu Corporation, model: CFT-50).
0) and measured using a 1φ x 10mm nozzle under the conditions of 170° C. and 100 kgf/cm 2 load.

(1) Tensile Strength The obtained vinyl chloride resin composition was fed to an 8-inch roll at 160°C, and after the composition was wound around the roll, it was melt-kneaded for 3 minutes to obtain a roll sheet. After preheating the obtained roll sheet at 170°C for 3 minutes, it was heated to 50Kg/cm.
2 for 4 minutes, and then cold pressed to obtain a vinyl chloride resin plate with a thickness of 2 mm. JI using the obtained resin plate
Measured according to SK6745. ■ After leaving the same vinyl chloride resin plate used for measuring tack tensile strength in an atmosphere of 70°C and 95% RH for one week,
The state of the surface was sensory tested in an atmosphere of 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 the same vinyl chloride resin plate as used for the measurement of tensile strength, the surface hardness was measured with a Shore hardness meter (manufactured by Uejima Seisakusho, model: HD-103N).

2. Physical properties of glass/vinyl chloride resin integrated moldings ■ Short shot resistance The obtained glass/vinyl chloride resin integrated moldings were visually observed and short shot resistance was evaluated according to the following criteria. . ○: The molded article of the vinyl chloride resin composition at the glass periphery exists without any chipping. ×: Part of the molded product of the vinyl chloride resin composition at the glass periphery is missing and exists in a short shot state■ The glass/vinyl chloride resin composition integral molded product with tack properties is heated at 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 is sticky and has tackiness.

Examples 1 to 7, Comparative Examples 1 to 5 Predetermined amounts of vinyl chloride resin, plasticizer, carboxylic acid, and barium-zinc liquid stabilizer (manufactured by Adeka Argas Co., Ltd., trade name: AC) shown in Table 1 were used. -190) 1.5 parts, barium-zinc powder stabilizer (manufactured by Adeka Argas Co., Ltd., trade name: AP-
550) and 3.0 parts of an organic epoxy compound stabilizer (manufactured by Adeka Argas Co., Ltd., trade name: O-130P) in a super mixer (manufactured by Kawada Seisakusho Co., Ltd., model: SMG-1).
00) and stirred 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: CO-100), stirred for 15 minutes, and stirred for 15 minutes.
A compound was obtained by cooling to below 0°C.

The obtained compound was supplied to an extruder (model: SLM-50, manufactured by Nagata Seisakusho Co., Ltd.) 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.

[0034] 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 0 kg/cm2 into the cavity.

Next, the mold is cooled by flowing cooling water through the cooling water pipe for cooling the mold, and the molten vinyl chloride resin composition in the cavity is cooled and solidified, and then the mold is opened and taken out, and the glass is - 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.

Examples 8 to 13, Comparative Examples 6 and 7 Predetermined amounts of vinyl chloride resin, plasticizer, fatty acid aryl ester, and barium-zinc liquid stabilizer (manufactured by Adeka Argas Co., Ltd., trade name; AC-190) 1.5 parts, barium
Zinc-based powder stabilizer (manufactured by Adeka Argas Co., Ltd., product name: A
P-550) 0.5 part and organic epoxy compound stabilizer (manufactured by Adeka Argas Co., Ltd., trade name: O-130P) 3.0
A vinyl chloride-based resin composition was obtained in the same manner as in Example 1 using a composition consisting of 1.5% and 1.0%, and a glass/vinyl chloride-based resin integrally molded article was obtained. Further, each physical property was measured in the same manner as in Example 1, and is shown in Table 2.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

Effects of the Invention The structure of the vinyl chloride resin composition of the present invention is as described above, and the vinyl chloride resin composition according to claim 1 comprises a vinyl chloride resin, a specific plasticizer,
The vinyl chloride resin composition according to claim 2 contains a specific dicarboxylic acid and/or tricarboxylic acid, and the vinyl chloride resin composition according to claim 2 contains a specific aliphatic aryl ester instead of the carboxylic acid. The molded product surface produced using the vinyl chloride resin composition has no tackiness and has excellent surface hardness.

[0040] The glass/vinyl chloride resin integrally molded article according to claim 3 is one in which the vinyl chloride resin composition according to claim 1 or claim 2 is injection molded on the peripheral edge of glass. The vinyl chloride resin composition exhibits excellent fluidity during injection molding, and the vinyl chloride resin composition completely wraps around the glass periphery without increasing the injection pressure, mold clamping pressure, etc., creating a short shot state. A glass with no missing parts of the vinyl chloride resin composition on the periphery of the glass.
A vinyl chloride resin integral molded body can be obtained, and the surface of the vinyl chloride resin molded body of the obtained glass/vinyl chloride resin integral 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 manufacturing the glass/vinyl chloride resin integrally molded article of claim 3 by injection molding. be.

[Explanation of symbols]

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

Claims (3)

[Claims] Claim 1: 100 parts by weight of vinyl chloride resin, 2 parts by weight of plasticizer
0 to 150 parts by weight and 0.5 to 10 parts by weight of a dicarboxylic acid represented by general formula (1) or/and a tricarboxylic acid represented by general formula (2).
Vinyl chloride resin composition for integral molding with vinyl chloride resin. [Formula 1] (In the formula, n represents an integer of 2 to 34.) [Formula 2] (In the formula, m represents an integer of 0 to 32.) 2. A glass comprising 100 parts by weight of a vinyl chloride resin, 20 to 150 parts by weight of a plasticizer, and 0.5 to 10 parts by weight of a fatty acid aryl ester represented by the general formula (3).
Vinyl chloride resin composition for integral molding with vinyl chloride resin. embedded image (In the formula, R1 represents an alkyl group having 5 to 30 carbon atoms, and R2 represents a phenyl group, an α-naphthyl group, or a β-naphthyl group.) 3. A glass/vinyl chloride resin integral body, characterized in that the vinyl chloride resin composition according to claim 1 or 2 is injection molded and integrally formed on the peripheral edge of the glass. Molded object.