JPH06107888A - Plastigel composition - Google Patents

Abstract

PURPOSE:To obtain a plastigel composition from which a soft molding in any shape can easily be produced with an orifice having a simple opening shape by mixing a specific vinyl chloride resin, a plasticizer, and silicic anhydride and regulating the viscosity of the mixture to a specific value. CONSTITUTION:The composition comprises, as the essential ingredients, 100 pts.wt. vinyl chloride resin obtained by fine-suspension polymerization using an emulsifier system comprising a plasticizer and at least either of an 8-20C alkylsulfuric acid and a salt of an 8-20C alpha-olefin sulfuric acid, 40-80 pts.wt. plasticizer, and 1-20 pts.wt. silicic anhydride having an average particle diameter of 0.5mum or smaller. Its viscosity at 23 deg.C is 50-5,000,000cP at a shear rate of 1sec<-1> and is 500,000cP or lower at a shear rate of 100sec<-1>. By the use of this composition, not only glass breakage can be prevented but also gasket attachment to a large-sized glass member can easily be conducted.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel plastigel composition, and more specifically, by a method such as extrusion under normal pressure without using expensive molds and injection equipment.
The present invention relates to a plastigel composition capable of easily producing a soft molded product having an arbitrary shape with a simple shape of a discharge mouthpiece.

[0002]

2. Description of the Related Art Generally, a gasket made of synthetic resin or rubber is attached to the periphery of window glass for automobiles for the purpose of sealing or decoration. Conventionally, this gasket is molded by a method such as melt extrusion, but since the molded product is a string shape, if it is bent too hard, the gasket will wrinkle and the appearance will be impaired. There was also a problem such as requiring labor. In order to solve such a problem, in recent years, a window glass has been placed in a molding die having a space formed in a peripheral portion thereof, and a gasket material such as synthetic resin or rubber is injected into the space portion in a molten state and cooled. After that, a method for producing a window glass with a gasket, which is taken out from the mold and integrated with a gasket material in the peripheral portion of the glass, has been attempted. However, in this method, since the synthetic resin and the rubber are melted and injected in a high viscosity state, there is a problem that the gasket material easily penetrates into the contact surface between the glass and the mold to cause burrs. In order to avoid this, if the mold is tightened to eliminate the gap, there is a problem that the glass is broken. Especially when the window glass is bent, it is difficult to make the curvature of the glass uniform.Therefore, when the mold is clamped, there are places where stress is applied intensively, which may lead to breakage. Many. Furthermore, when a synthetic resin or rubber is used as the gasket material, it is melted in the injection molding machine to impart fluidity and then injected into the mold, but since the viscosity in the molten state is high, injection at high pressure is recommended. It costs. As a result, the melt penetrates into the gap between the glass and the mold, and it becomes extremely difficult to prevent the occurrence of burrs. In order to solve the above problem, it has been proposed to use plastigel as a gasket molding material (Japanese Patent Laid-Open No. 122722/1989). In this method, a window glass is placed in a molding die, a cavity space for gasket molding is formed between the peripheral edge of the window glass and the inner surface of the molding die, and plastigel as a gasket forming material is injected into the space. , Which is solidified by heating. According to this method, since it is possible to inject at a low pressure, it is not necessary to tighten the glass further, so that it is possible to prevent the occurrence of burrs. However, even in this method, since the viscosity of the plastigel is low, it is conceivable that the gel may penetrate into the gap and cause burrs if the mold and the glass are not fastened tightly. Also, since plastigel is injected into the closed mold at a low pressure, unless the air escape area is devised considerably, it will be molded with air bubbles entrapped, which will impair the appearance and the strength of the product. There is a concern that problems will occur.

[0003]

SUMMARY OF THE INVENTION Under the circumstances, the present invention provides a simple discharge nozzle by a method such as extrusion molding under normal pressure without using an expensive mold or injection device. The purpose of the present invention is to provide a plastigel composition suitable for use as a gasket molding material and the like, because a soft molded article of any shape can be easily produced by the above shape.

[0004]

Means for Solving the Problems As a result of intensive studies to develop a plastigel composition having the above-mentioned preferable properties, the present inventors have found that a vinyl chloride resin and a plasticizer obtained by a specific polymerization method. And a silicic acid anhydride are contained at a predetermined ratio as an essential component, and by a plastigel composition having a specific viscosity, it has been found that the object can be achieved.
The present invention has been completed based on this finding. That is, the present invention was obtained by the fine suspension polymerization method using (A) an alkyl sulfate having 8 to 20 carbon atoms and / or an α-olefin sulfate having 8 to 20 carbon atoms and a plasticizer as an emulsifier system. 100 parts by weight of vinyl chloride resin, (B) plasticizer 40-8
0 parts by weight and (C) 1 to 20 parts by weight of silicic acid anhydride having an average particle size of 0.5 μm or less are essential components, and the viscosity at a temperature of 23 ° C. is 500,000 to 5,000,000 c at a shear rate of 1 sec ^−1.
It is intended to provide a plastigel composition characterized by having a ps and a shear rate of 100 sec ⁻¹ of 500,000 cps or less.

The present invention will be described in detail below. The plastigel composition of the present invention is a dispersion containing vinyl chloride resin, a plasticizer, and silicic acid anhydride as essential components, and is usually a high-viscosity composition that does not flow-deform under its own weight. The vinyl chloride resin is a vinyl chloride homopolymer or a copolymer of vinyl chloride and another monomer, and has a primary particle size of 0. 0 obtained by a fine suspension polymerization method using a specific emulsifier system described later.
It is a fine particle polymer of 01 to 10 μm and is used for plastisol or plastigel processing. Moreover, the thing which aggregated it may be contained. As a method of aggregating vinyl chloride resin, polymer latex is acidized,
There are methods such as salt, electrolysis (electrolysis), centrifugation, floating, dialysis, and heat, which destroy the stability to coagulate and dry, and spray drying to agglomerate.

The vinyl chloride resin used as the component (A) in the composition of the present invention comprises an alkylsulfate having 8 to 20 carbon atoms and / or an α-olefin sulfate having 8 to 20 carbon atoms, and a plasticizer. It is obtained by a fine suspension polymerization method using as an emulsifier system. Examples of the alkyl sulfate having 8 to 20 carbon atoms and the α-olefin sulfate having 8 to 20 carbon atoms include alkali metal salts such as sodium salt and potassium salt, ammonium salt, triethanolamine salt and the like. As a raw material of the alkyl sulfate or α-olefin sulfate, for example, a natural one such as coconut oil or palm oil, or a synthetic alcohol based on petroleum is used. These emulsifiers may be used alone or in combination of two or more,
The amount used is usually selected in the range of 0.2 to 2.0 parts by weight, preferably 0.5 to 1.0 parts by weight, per 100 parts by weight of the monomer used.

On the other hand, examples of the plasticizer used in combination with the emulsifier include (1) phthalic acid alkyl ester plasticizers such as dioctyl phthalate, dinonyl phthalate, butyl lauryl phthalate and methyl oleyl phthalate,
(2) Aromatic carboxylic acid ester plasticizers such as trioctyl trimellitate and diethylene glycol dibenzoate, (3) Aliphatic dibasic acid ester plasticizers such as dioctyl adipate, dibutyl sebacate and dioctyl tetrahydrophthalate, (4 ) Phosphate ester plasticizers such as trioctyl phosphate and trichloroethyl phosphate, (5) Diethylene glycol dicaprylate, aliphatic glycol ester plasticizers such as 1,4-butylene glycol-di-2-ethylhexanoate Agent and (6) polyester plasticizer, (7) butyl oleate, methyl acetylricinoleate, 2,2,4-
Fatty acid ester type such as trimethyl-1,3 pentanediol diisobutyrate, epoxidized soybean oil, epoxy type such as octyl epoxystearate, chlorinated paraffin type such as chlorinated fatty acid methyl, chlorinated paraffin and dioctyl succinate Examples thereof include aliphatic dibasic acid ester-based secondary plasticizers, (8) petroleum-based diluents such as mineral spirits and mineral terpenes, and linear alkylbenzene-based diluents such as dodecylbenzene.

One of these plasticizers may be used, or 2
You may use in combination of 2 or more types, and the usage-amount is 0.2-3.0 weight part with respect to 100 weight part of monomers normally used, Preferably it selects in the range of 0.5-2.0 weight part. Be done.
Further, the vinyl chloride resin has a primary particle size of 0.01 to 0.01, which comprises a vinyl chloride homopolymer obtained by fine suspension polymerization or a copolymer of vinyl chloride and another monomer, using the emulsifier system. There is no particular limitation as long as they are fine particles of 10 μm and can be used for plastisol or plastigel processing. Examples of other monomers include ethylene-based hydrocarbons, fatty acid vinyls, acrylic acid esters, vinyl ethers, vinylidene halides, and allyl compounds. Examples of the ethylene hydrocarbons include ethylene, propylene and isobutylene, and examples of the fatty acid vinyls include vinyl acetate, vinyl caproate, vinyl pelargonate, vinyl laurate, vinyl myristate, vinyl palmitate, and acrylic acid. Examples of the ester include methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, and acrylic acid-2.
-Hydroxyethyl and the like.

Examples of vinyl ethers include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl-n-butyl ether and cetyl vinyl ether, and examples of vinylidene halides include vinylidene chloride and vinylidene fluoride.
Examples of the allyl compound include allyl halides such as allyl chloride and allyl bromide, alkyl ethers of allyl alcohol such as methyl allyl ether and ethyl allyl ether, ethylene glycol monoallyl ether,
(Poly) oxyalkylene ethers of allyl alcohol such as propylene glycol monoallyl ether, polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether, allyl carboxylic acids such as vinyl acetic acid and undecenoic acid, allyl alcohol such as allyl acetate and allyl butyrate Allylphenols such as esters, eugenol, isoeugenol,
Allyl thiol and its ethers, esters, N, N
-Allylamine such as dimethylallylamine and allylamine, and salts thereof. These other monomers may be used alone or in combination of two or more.

Examples of the plasticizer used as the component (B) in the composition of the present invention include phthalic acid compounds such as dioctyl phthalate (DOP), dihexyl phthalate (DHP), diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP). Ester, dioctyl adipate (DOA), dioctyl sebacate (DO
S) such as fatty acid ester, polyester such as condensate of adipic acid and polyethylene glycol, acrylic acid ester, methacrylic acid ester, and phosphoric acid ester such as tricresyl phosphate (TCP), and if necessary, reaction Mention may be made of plasticizers which can usually be used for processing polyvinyl chloride, such as plasticizers. These plasticizers may be used alone or in combination of two or more, and the amount thereof is 40 to 80 parts by weight per 100 parts by weight of the vinyl chloride resin as the component (A). Must be in range. If this amount is less than 40 parts by weight, the molded product will be too hard, and if it exceeds 80 parts by weight, the viscosity at a temperature of 23 ° C. will be 500,000 ^- at a shear rate of 1 sec ^−1.
To achieve 5,000,000 cps, especially 1,000,000 cps or more, a large amount of filler must be used, resulting in an unfavorable situation such as an increase in hardness of the molded product and deterioration of its physical properties.

In the composition of the present invention, silicic acid anhydride having an average particle size of 0.5 μm or less is used as the component (C). The amount of the silicic acid anhydride to be used needs to be in the range of 1 to 20 parts by weight per 100 parts by weight of the vinyl chloride resin as the component (A). If this amount is less than 1 part by weight, the temperature is 2
Viscosity at 3 ° C is 500,000-50 at a shear rate of 1 sec ^-1.
A large amount of other fillers and the like must be used in order to attain the level of 100,000 cps, especially 1 million cps or more, and as a result, the hardness of the molded product increases and the physical properties deteriorate, which causes an unfavorable situation. Further, if it exceeds 20 parts by weight, the viscosity becomes too high and molding cannot be performed. Further, a blend resin for processing a vinyl chloride paste may be added for the purpose of suppressing the thread-forming property of the plastigel. The blended resin is a vinyl chloride homopolymer or copolymer having an average particle size of 10 to 60 μm, and the addition amount thereof is the vinyl chloride resin 10 as the component (A).
It is 2 to 50 parts by weight per 0 parts by weight. If necessary, various compounding agents for vinyl chloride resins such as fillers, diluents, stabilizers, pigments and ultraviolet absorbers can be added to the plastigel composition of the present invention. Examples of the filler include calcium carbonate, mica, talc, kaolin clay, celite, asbestos, perlite, baryta, silica, silica sand, flake graphite, dolomite limestone,
Examples thereof include gypsum, fine aluminum powder, inorganic fine particles such as calcium carbonate, organic / inorganic composite thixotropic agent, and organic thixotropic agent. Examples of the thixotropic agent include silicic acid anhydride (mean particle size: 0.5 μm).
m)), silicic acid such as hydrous silicic acid, bentonite such as organic bentonite, asbestos such as cyclodex, and organic such as dibenzylidene sorbitol. These fillers are appropriately added to the composition depending on the application.

On the other hand, as a method of increasing the viscosity, there is a method of dissolving a polymer substance such as rubber or resin in a plasticizer.
Preferred dissolved polymers include polyvinyl chloride and NB
R, EVA, and the like can be used, and other substances that are soluble in a plasticizer and can increase the viscosity can also be used.
As another method for increasing the viscosity, there is a method in which a dispersion of a vinyl chloride resin and a plasticizer is heat-treated to appropriately absorb and swell the plasticizer in the vinyl chloride resin. Since the dispersion of the vinyl chloride resin and the plasticizer will gel if heated too much, it is necessary to heat the dispersion appropriately. Moreover, you may bridge | crosslink etc. as needed. Although any of the above methods may be used, the viscosity of the plastigel composition of the present invention at a temperature of 23 ° C. is 500,000 to 500 at a shear rate of 1 sec ⁻¹ .
10,000 cps, 500,000 cp at a shear rate of 100 sec ^-1
It must be s or less. If the shear rate is less than 500,000 cps at a shear rate of 1 sec ^-1 , it may flow when the plastigel composition is filled in the mold and flow out from the open part. If it is more than 5 million cps, the fluidity may be poor. It is difficult to discharge. Also, the shear rate is 100 sec
^-1 above 500,000 cps, the supply pipe resistance is large, and the supply pressure must be increased, so that not only the easy molding which is the object of the present invention cannot be achieved but also the dischargeability is inferior and any It will not be possible to eject into shape.

In the plastigel composition of the present invention, the above-mentioned component (A), component (B), component (C) and various additives used as necessary are mixed in a known manner by a planetary mixer, a kneader, a roll or the like. It can be prepared by homogeneously mixing and stirring using a machine. Next, as an example of molding using the plastigel composition thus obtained, molding and adhering a gasket to the peripheral portion of glass will be shown. When formed on the entire peripheral portion of the glass, the discharge start portion and the discharge end portion are discontinuous, but since the plastigel composition can easily give a shape, it is easy to correct it with a spatula or the like into a continuous shape. is there. After the plastigel composition is attached to the peripheral portion, the composition is melted by heating and develops strength by cooling to room temperature. As the heating method, for example, hot air, high frequency dielectric heating, high frequency induction heating, or any other method used for melting the plastigel can be used, but it is necessary to provide sufficient heat for melting. Moreover, you may bridge | crosslink etc. as needed.

Further, it is desirable that the plastigel composition of the present invention has adhesiveness to glass. In order to impart adhesiveness to the plastigel composition, the vinyl chloride resin may be a copolymer of vinyl chloride and another functional group-containing monomer. Examples of the functional group-containing monomer include 2
Examples thereof include hydroxyl group-containing monomers such as hydroxypropyl methacrylate, epoxy group-containing monomers such as glycidyl methacrylate, carboxyl group-containing monomers such as maleic anhydride, and amino group-containing monomers such as dimethylaminoethyl methacrylate. Adhesiveness to glass can be imparted by mixing these copolymers alone or with an ordinary vinyl chloride resin. Further, in order to increase the adhesive strength, a cross-linking agent depending on the type of functional group can be used together. Another method of imparting adhesiveness is applying a primer to the glass surface. Adhesiveness can be imparted by previously applying an adhesion primer to the portion to which the gasket is attached. Furthermore, as a method of imparting another adhesiveness, a method of adding an adhesiveness imparting agent to the plastigel composition can be mentioned. Examples of the adhesiveness-imparting agent include polyethyleneimine, polyamide resin, and epoxy resin. The adhesive is considered to be developed by the reaction between the hydroxyl group on the glass surface and the functional group or hydrogen bonding. The adhesive strength can be determined by a 90 ° peel test. The adhesive strength is preferably 0.1 kg / cm (tensile strength 200 mm / min) or more, and particularly preferably 1 kg / cm or more.

[0015]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Examples 1 and 2, Comparative Examples 1 to 5 Components of the types and amounts shown in Table 1 were mixed in a Hobart mixer and defoamed to prepare a plastigel composition, and the following items were evaluated. The vinyl chloride resins (1), (2) and (3) in the table are obtained as follows. Vinyl chloride resin (1) Using 0.5 parts by weight of sodium lauryl sulfate and 3.0 parts by weight of dioctyl phthalate as an emulsifier, 95 parts by weight of vinyl chloride and 5 parts by weight of vinyl acetate were subjected to fine suspension polymerization at 41 ° C. Obtained average degree of polymerization 1700, average particle size 1.
It is a vinyl chloride resin of 0 μm. Vinyl chloride resin (2) 100 parts by weight of vinyl chloride is finely suspended at 41 ° C. by using 0.8 parts by weight of Lipolan 1400 [Lion Co., Ltd., trade name] and 2.0 parts by weight of chlorinated paraffin as an emulsifier. The average degree of polymerization obtained by polymerization is 1800, and the average particle size is 0.3 μm.
Vinyl chloride resin. Vinyl chloride resin (3) An average obtained by finely suspension-polymerizing 100 parts by weight of vinyl chloride at 41 ° C., using 0.5 parts by weight of sodium dodecylbenzenesulfonate as an emulsifier and 2.0 parts by weight of chlorinated paraffin. It is a vinyl chloride resin having a degree of polymerization of 1800 and an average particle size of 0.3 μm.

Evaluation item (1) Shape after heating FIG. 1 shows an apparatus for directly discharging the plastigel composition to the peripheral edge of the glass and a plastigel on the peripheral edge of the glass while discharging the plastigel composition from a gun mouthpiece having a predetermined shape. It is a perspective view which shows the state which has made the composition adhere. Put the plastigel composition in a tank, pressurize it with a snake pump, and through the hose 4 with an inner diameter of 10 mm, the gun discharge mouthpiece 3
As shown in 2, discharge at 50cc / min, 30cm ×
While moving to the periphery of the glass 1 with a thickness of 50 cm x 3 mm, the maximum thickness in the vertical direction of the glass surface is 20 mm, and the width in the horizontal direction is 10 mm.
The plastigel composition of 1 was attached and heated in a hot air oven at 180 ° C. for 15 minutes. Then, it was cooled to near room temperature, and the shape after heating was visually evaluated. (2) Viscosity The viscosity at a shear rate of 1 sec ^-1 and a shear rate of 100 sec ^-1 was measured using a Rotovisco rotary viscometer. Control console: HAAKE ROTOVIS
CO RV-3 sensor: cone-plate type PK-2 These results are shown in Table 1.

[0018]

[Table 1]

Note) Zeon resin 54J: Nippon Zeon Co., Ltd., blend resin for processing polyvinyl chloride paste Vinyl chloride-vinyl acetate (11% by weight) copolymer, average particle size 40 μm Calseeds PL: Kamijima Chemical Industry Co., Ltd. Made, finely divided calcium carbonate, average particle size 0.1 μm Aerosil # 300: Nippon Aerosil Co., Ltd., anhydrous silica

In each of Example 1 and Example 2, the plastigel composition was smoothly discharged from the discharge mouthpiece, the cross-sectional shape maintained a predetermined shape, the shape did not change even after heating, and both the appearance was improved. We were able to obtain a windowpane with a satisfactory gasket. In Comparative Example 3, the plastisol was smoothly discharged from the discharge mouthpiece, but the desired shape could not be maintained and the plastisol flowed out immediately. In Comparative Example 2 and Comparative Example 4, ejection could not be performed.

[0021]

EFFECTS OF THE INVENTION According to the present invention, a soft molded product of any shape can be formed by a simple shape of the discharge die by a method such as extrusion molding under normal pressure without using an expensive mold and injection device. A plastigel composition is obtained which is easily manufactured. Further, by using this plastigel composition, not only can glass be prevented from being broken, but a gasket can be easily added to a large glass.

[Brief description of drawings]

FIG. 1 is a diagram showing a method for manufacturing a window glass with a gasket for shape evaluation after heating in Examples and Comparative Examples.

[Explanation of symbols]

 1 Glass 2 Discharged Plastigel Composition 3 Gun Discharge Porter 4 Plastigel Composition Supply Hose

Claims (1)

[Claims] 1. A chloride obtained by a fine suspension polymerization method using (A) an alkyl sulfate having 8 to 20 carbon atoms and / or an α-olefin sulfate having 8 to 20 carbon atoms and a plasticizer as an emulsifier system. 100 parts by weight of vinyl resin, (B) plasticizer 40-80
Parts by weight and (C) 1 to 20 parts by weight of silicic acid anhydride having an average particle size of 0.5 μm or less are essential components, and the viscosity at a temperature of 23 ° C. is 500,000 to 5,000,000 cp at a shear rate of 1 sec ^−1.
s and a shear rate of 100 sec ⁻¹ is 500,000 cps or less.