JPH0586247A - Plastigel composition and molded body using the same composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition capable of readily and accurately providing a molded product free from burr by a simple apparatus under ordinary pressure and molding also into a shape having a thin part by dispersing a vinyl chloride based resin with a filler each having a specified particle diameter into a plasticizer. CONSTITUTION:The objective composition is a plastigel obtained by dispersing (A) 100 pts.wt. vinyl chloride based resin having <=5mum average uniform particle diameter and (B) 20-100 pts.wt. filler (e.g. calcium carbonate or mica) having <=0.5mum average uniform particle diameter into (C) 40-80 pts.wt. plasticizer (e.g. diisononyl phthalate), having a viscosity at ordinary temperature of 50000-5000000CPS/1sec shearing rate and <=500000CPS/100sec shearing rate, and a melt viscosity of >=100000CPS at 180 deg.C. There is e.g. a method for dissolving a polymer such as PVA in the component C or a method for heating a dispersed product of the components A and C to properly absorb and swell the component C into the component A, in order to make the composition highly viscous.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a simple discharge mouthpiece by a method such as extrusion molding under normal pressure without using an expensive mold and a high-pressure injection device, and has an arbitrary shape, particularly a thin wall thickness. The present invention relates to a plastigel composition capable of easily manufacturing a flexible molded product having a shape having a portion.

[0002]

2. Description of the Related Art Generally, a gasket made of synthetic resin or rubber is attached to a peripheral portion of a window glass of an automobile or the like 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 deteriorate, and it will be difficult to install. There was a problem. Further, there is a problem that it requires manpower. In order to solve this problem, for example, an automobile window glass is placed in a molding die having a space formed in its peripheral portion, and a gasket material such as synthetic resin or rubber is injected into the space portion in a molten state and cooled. After that, it is taken out from the mold and a method of manufacturing a window glass with a gasket in which a gasket material is integrated with the peripheral edge of the glass is proposed. However, in this method, since the synthetic resin or rubber is injected in a melted and highly viscous state, the gasket material has a drawback that it easily penetrates into the contact surface between the glass and the mold to cause burrs. In order to avoid this, if the mold is strongly tightened to eliminate the gap, there is a problem that the glass is broken. In particular, when the window glass is bent, it is difficult to make the curvature of the glass uniform, and therefore, when the mold is tightened, there are places where stress is intensively applied, which may lead to breakage. Many. Furthermore, when synthetic resin or rubber is used as the gasket material, it is melted in the injection molding machine and given fluidity before it is injected into the mold, but it is necessary to inject at high pressure because the viscosity in the molten state is high. .. Therefore, high pressure is applied to the gap between the glass and the molding die, which makes it difficult to prevent burrs from occurring. In order to solve the above problems, it has been proposed to use plastisol as a gasket molding material (JP-A-1-122722). In this method, a window glass is placed in a molding die, a cavity space for gasket molding is formed between the peripheral portion of the window glass and the inner surface of the molding die, and plastisol as a gasket forming material is injected into the space. This is a method of heating and solidifying. According to this method, since the molding can be performed at a low pressure, it is considered that it is easy to prevent burrs from being generated because it is not necessary to tighten the periphery of the window glass portion so much. However, even with this method, if the mold and glass are not tightly clamped, gel may penetrate into the gap and cause burr, and since the plastigel is injected into the sealed mold at low pressure, air bubbles will be generated. There is a risk that the product will be molded in a state where it is rolled up, which may impair the external appearance or cause a problem in the strength of the product. Further, for example, when the gasket has a thin-walled portion having a thin wall thickness of about 0.5 to 2 mm, there is a drawback that this portion is often deformed and molded.

[0003]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a plastigel which can easily prevent burrs from being formed in the above molding method and can be molded into any shape, especially a shape having a thin wall portion. It is intended.

[0004]

DISCLOSURE OF THE INVENTION The present inventors believe that the drawbacks of the plastigel depend on the viscoelastic properties of the plastigel. Is essential, and when the diameter of the particles added to the plastigel is reduced, the effective surface area increases, the plasticizer bound to the particle surface increases, and the plasticizer that contributes to the fluidity decreases conversely and the viscosity increases. Based on this finding, we found that if we control the high viscosity of plastigel by selecting the compounding amount of fine particles and the particle size, we can solve the problems of burr formation and bubbles. The invention was completed.
That is, according to the present invention, 100 parts by weight of a vinyl chloride resin having an average single particle size of 5 μm or less and an average single particle size of 0.5 μm are used.
It is a plastigel in which 20 to 100 parts by weight of the following fillers are dispersed in 40 to 80 parts by weight of a plasticizer and has a viscosity at room temperature of 500,000 cps or more at a shear rate of 1 sec ^-1 .
0,000 cps or less, 500,000 cps at a shear rate of 100 sec ^-1
It has the following viscosity and a melt viscosity at 180 ° C of 100,000.
The present invention provides a plastigel composition having cps or more and a molded article obtained by extrusion-molding the composition at normal pressure and then heating.

The plastigel of the present invention is a plastigel having a high viscosity such that it does not deform under its own weight when left for a short time at room temperature. This means that the plastigel of the present invention has a viscosity at room temperature of 500,000 cps at a shear rate of 1 sec ^-1. More than 50
0,000 cps or less, 500,000 cps at a shear rate of 100 sec ^-1
It is indicated by having the following viscosity: The vinyl chloride resin having an average single particle size of 5 μm or less used in the present invention is a vinyl chloride homopolymer or a copolymer with 50% by weight or less of another monomer, and is obtained by emulsion polymerization or fine suspension polymerization. It is a fine-grained polymer having an average primary particle size of 5 μm or less, which is used for plastisol or plastigel processing.

It is essential that the vinyl chloride resin used in the present invention has an average single particle size of 5 μm or less. For example, when the plastigel has a sufficiently high viscosity under other conditions, this vinyl chloride resin is The resin can be replaced with a vinyl chloride resin having an average single particle size of more than 5 μm in a range of 50% by weight or less. As described above, a resin partially substituted with a vinyl chloride resin having a large average particle diameter also corresponds to the definition of the vinyl chloride resin having an average single particle diameter of 5 μm or less in the present invention. Therefore, the amount of the vinyl chloride-based resin defined above in the plastigel of the present invention includes the amount of the resin having a large particle size, which is partially replaced.

When the vinyl chloride resin having an average single particle diameter of more than 5 μm is 50% by weight or more, the viscosity at room temperature is in the range of 500,000 cps or more and 5,000,000 cps or less at a shear rate of 1 sec ^-1 , and therefore, especially 100 In order to obtain 10,000 cps or more, a large amount of filler or the like must be used, and such a high viscosity will not be obtained. As a result, the hardness will increase and the physical properties of the soft molded article will be lost. Further, the vinyl chloride resin having an average single particle diameter of 5 μm or less used in the present invention is a concept including an aggregate of particles having an average single diameter of 5 μm or less, and this aggregate is also preferably used in the present invention. be able to. As a method of coagulating vinyl chloride resin, polymerized latex is solidified by acid, salt, electrolysis (electrolysis), centrifugation, suspension, dialysis, heat, etc. to break the stability of the latex, and then dried or spray-dried particles. There is a method of aggregating into a shape.

The plasticizer used in the present invention is DOP or DH.
Phthalates such as P, DINP, DIDP, D
Plasticizers such as OA, DOS and other fatty acid-based esters, polyesters such as condensates of adipic acid and polyethylene glycol, acrylic acid esters, methacrylic acid esters, and phosphoric acid esters such as TCP, which are usually used for polyvinyl chloride processing, may be used alone or Used as a mixture. The filler used in the present invention includes calcium carbonate, mica, talc, kaolin clay, celite, asbestos, perlite, baryta, silica, silica sand, scaly graphite, dolomite limestone, gypsum, aluminum fine powder, silicic acid anhydride, calcium carbonate and the like. Particulate inorganic materials, organic / inorganic composite thixotropic agents, organic thixotropic agents, etc. An organic material such as sorbitol can be used, and it is used by adding it to the composition of the polyvinyl chloride resin and the plasticizer.

A filler having an average single particle size of 0.5 μm or less is essential for the filler used in the present invention. For example, when the high viscosity required for the plastigel of the present invention is obtained by other conditions, It is also possible to replace the same or other type of filler having an average single particle size of more than 0.5 μm in the range of 50% by weight or less. Such replacement of a part of the filler with a large particle size also corresponds to the concept of the filler of the present invention. Therefore, the amount of the filler used in the plastigel of the present invention includes the substituted filler having a large particle size. When the filler having an average single particle size of more than 0.5 μm is 50% by weight or more, the viscosity at room temperature has a shear rate of 1 se.
c ^-1 to 500,000 cps to 5 million cps, especially 1 million cps
In order to achieve the above, a large amount of filler or the like must be used, and as a result, there arises a problem that hardness is increased and physical properties are deteriorated. Further, addition of a filler having a small average single particle size has the effect of improving the viscosity while suppressing the viscoelastic behavior during extrusion molding and improving the dimensional accuracy of the molded body.

The viscosity of the plastigel of the present invention can be changed by the particle size and content of the particles dispersed in the plastigel and the amount of the plasticizer. INDUSTRIAL APPLICABILITY The present invention is a vinyl chloride having an average single particle diameter of 5 μm or less, which is used under the determined conditions such as the amount of resin and the ratio of plasticizer, type of plasticizer, other additives, etc. Particle size and amount of base resin and
It is characterized in that the viscosity of the plastigel is adjusted to a specific high viscosity by appropriately selecting the particle size and the blending amount of the filler of 5 μm or less.

The plastigel of the present invention has an average single particle size of 0.5 with respect to 100 parts by weight of the vinyl chloride resin in the plastigel in order to achieve a high viscosity under the above-mentioned conditions.
20-100 parts by weight of a filler having a size of less than or equal to μm and a plasticizer 40-
It can be blended in the range of the ratio of 80 parts by weight.
In this case, if the blending ratio of the filler is less than 20 parts by weight,
It becomes difficult to increase the viscosity of the plastigel, and if it is more than 100 parts by weight, the thixotropy is deteriorated, and the shape of the shaped gel tends to collapse before being fixed by heating. Also,
If the compounding ratio of the plasticizer is more than 80 parts by weight, the viscosity of the plastigel is too low, and if it is less than 40 parts by weight, the viscosity of the plastigel is too high.

As a method for increasing the viscosity of the plastigel of the present invention, a method of dissolving a polymer such as rubber or resin, which is optionally added, in a plasticizer may be supplementarily used. Preferred dissolving polymers include polyvinyl chloride, NBR, EVA and the like. As long as it is soluble in other plasticizers and can increase the viscosity, it can be used without particular limitation. Furthermore, as another method of increasing the viscosity, a dispersion of a vinyl chloride resin and a plasticizer is added,
A method in which the plasticizer is appropriately heat-treated to absorb and swell the polyvinyl chloride resin can be used in combination. If the dispersion of polyvinyl chloride and the plasticizer is heated too much, it will gel, so it is necessary to heat it appropriately. In addition, compounding agents that are usually used for processing polyvinyl chloride, such as diluents, stabilizers, pigments, and ultraviolet absorbers, can be optionally used. Other optional additives such as diluents, stabilizers, ultraviolet absorbers, titanium dioxide, litharge, lithopone, zinc oxide, pigments such as carbon, etc. can be optionally used in combination with polyvinyl chloride. Also changes the viscosity of the plastigel.

The plastigel composition of the present invention has various average compounds having an average single diameter so as to be a highly viscous product in the above viscosity range, depending on various compounds and resin contents which are added to plastigel depending on the required properties to affect the viscosity. By selecting the blending amount of the resin particles of 5 μm or less and the blending amount of the filler of 0.5 μm or less, the plastigel of the present invention can always have a specific high viscosity. In the present invention, the viscosity of plastigel at room temperature is 500,000 cps or more at a shear rate of 1 sec ^-1.
0,000 cps or less, 500,000 cps at a shear rate of 100 sec ^-1
It should have the following viscosity: If the viscosity of the plastigel is less than 500,000 cps at a shear rate of 1 sec ^-1 , there is a risk that the plastigel will flow and flow out from the open part when the plastigel is filled in the mold. On the other hand, if it is more than 5 million cps, the fluidity is poor and it becomes impossible to discharge at normal pressure. If the shear rate is more than 500,000 cps at a shear rate of 100 sec ^-1 , the supply pipe resistance is large and the supply pressure must be increased, which not only prevents the easy molding, which is the object of the present invention, The dischargeability is inferior, and it becomes impossible to mold into an arbitrary shape.

Further, in the present invention, the plastigel composition must have a melt viscosity at 180 ° C. measured by a rheometrics dynamic spectrometer of 100,000 cps or more. When the viscosity is less than 100,000 cps, deformation occurs when the gasket of the molded product has a thin wall portion. That is, a thin wall portion having a thickness of 0.5 to 2 mm (for example, an arrow portion in FIG. 2) can also be formed without causing deformation such as waviness and widening or narrowing of the cross-sectional width. 180
If the melt viscosity at 100 ° C. is less than 100,000 cps, the plastigel will flow during heat molding and the shape of the molded product will change. The composition of the present invention can be produced by mixing and stirring the respective components, the composition of which has been determined according to the above concept, with a known mixer such as an existing planetary mixer, kneader or roll.

The plastigel of the present invention can be formed by attaching a gasket to the periphery of the glass by using an extruder as shown in FIG. 1, for example. When formed on the entire periphery of the glass, the discharge start part and discharge end part become discontinuous, but since plastigel can easily give shape, it is possible to easily correct the seam to a continuous curved surface with a spatula etc. it can. After the plastigel of the present invention is attached to the peripheral portion, it is once melted by heating and then cooled to room temperature to fix the shape and increase the strength of the molded body. Despite the extruded product of high viscosity, this molded product has good dimensional accuracy and a product having a certain designed size can be obtained. The heating method is not particularly limited as long as it provides a sufficient amount of heat for melting, and it can be performed by any method used for melting plastisol, such as hot air, high frequency dielectric heating, and high frequency induction heating.

Further, the plastigel used in the present invention is
It is desirable that this has adhesiveness to glass or the like that is formed by contact. In order to provide the plastigel of the present invention with adhesiveness to glass or the like, a method in which a vinyl chloride resin is a copolymer of vinyl chloride and another functional group-containing monomer can be used. Examples of functional group-containing monomers include hydroxyl group-containing monomers such as 2-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. Is mentioned. Adhesiveness to glass can be imparted by mixing these copolymers alone or with ordinary polyvinyl chloride. A cross-linking agent depending on the type of functional group may be used in combination for increasing the adhesive strength.

Another method of imparting adhesiveness to the plastigel of the present invention is to apply a primer to the surface of glass. Adhesion can be imparted by applying an adhesion primer in advance to the portion to which the gasket is attached.
As another method for imparting the adhesiveness of the plastigel of the present invention, there is a method of adding an adhesiveness-imparting agent into the plastigel. Examples of the adhesion-imparting agent include polyethyleneimine, polyamide resin, epoxy resin and the like.
It is considered that the adhesiveness by these methods is expressed by the reaction between the hydroxyl group present on the glass surface or the like and the functional group or the hydrogen bond.

The adhesive strength of the plastigel of the present invention is 90 °
It can be evaluated by a peel test. In the present invention,
This adhesive strength is 0.1 kg / cm (tensile strength 200 mm / mi
n) or more, particularly 1 kg / cm or more. By using all or part of the total vinyl chloride resin component used in the plastigel of the present invention in place of a vinyl chloride copolymer containing 2.5 to 50% by weight of another monomer unit, Adhesive plastigel can be produced.

[0019]

EXAMPLES The present invention will be described in more detail with reference to the following examples. Examples 1 to 4 and Comparative Examples 1 to 4 The respective raw materials shown in Table 1 were mixed with a Hobart mixer and defoamed to prepare plastigel. Each of the obtained plastigel was applied to two glass plates with a coating thickness of 3 mm and a coating width of 1
It was applied so as to have a size of 50 mm × 100 mm and heated in a hot air circulation type oven at 180 ° C. for 10 minutes. Various physical properties were measured and evaluated using the sheet thus obtained. The methods for measuring and evaluating physical properties are as follows.

<Hardness> The above sheet was cut into three 50 mm × 100 mm sheets, the three sheets were overlaid, and the hardness was measured by a spring type hardness test (A type). (JIS
(Refer to K-6301) <Tensile strength> According to JIS K-7113. <Shape after heating> FIG. 1 shows a device for directly ejecting plastigel to the peripheral edge of the glass according to the present invention, and a state in which the plastigel is attached to the peripheral edge of the glass while ejecting the plastigel from a gun mouthpiece having a predetermined shape. It is a perspective view showing. Reference numeral 1 is glass, 2 is a discharged plastigel, 3 is a gun discharge mouthpiece, and 4 is a plastigel supply hose. Put the above-mentioned plastigel in a tank, pressurize with a snake pump, discharge from a hose 4 having an inner diameter of 10 mmφ at 50 cc / min from a gun discharge nozzle 3, 30 cm × 50 cm × 3 m
While moving to the periphery of m-thick glass, a gel with a maximum thickness of 20 mm in the vertical direction of the glass surface and a width of 10 mm in the horizontal direction is attached, and the glass surface is kept horizontal in a hot air oven at 180 ° C.
Heated for 5 minutes. Then, it was cooled to near room temperature and the shape after heating was evaluated. Further, the maximum thickness of the molded product in the horizontal direction of the glass surface was measured.

<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 ROTOVISCO RV-3 Sensor: Cone plate type PK-2 <melt viscosity> Rheometrics dynamic spectrometer (Rheometrics) is used, and parallel plate 40mmφ is used, frequency 0.25Hz,
The melt viscosity of the composition was measured under the conditions of a plate gap of 3 mm, a temperature rising speed of 10 ° C./min, and a measurement temperature of 180 ° C. The evaluation results are shown in Table 1.

[0022]

[Table 1]

Note 1) Zeon resin 43F: vinyl chloride resin manufactured by Nippon Zeon Co., Ltd., average particle size 0.2 μm 2) Epoxy group-containing PVC: average particle size of 97% by weight vinyl chloride and 3% by weight glycidyl methacrylate.
2 μm, vinyl chloride resin having an average degree of polymerization of 1200 3) ZEON resin 121: vinyl chloride resin manufactured by Nippon Zeon Co., Ltd., average particle size 1.0 μm 4) ZEON resin 51: vinyl chloride resin manufactured by Nippon Zeon Co., Ltd.
3.5% by weight vinyl acetate copolymer, average particle size 40 μm 5) Epoxy resin: Bisphenol A manufactured by Asahi Denka Co., Ltd.
Epoxy resin E-4001 6) Polyethyleneimine: Polyethyleneimine SP-018 manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd. 7) Calseeds PL: Fine calcium carbonate manufactured by Kamishima Chemical Co., Ltd., average particle size 0.1 μm 8) Whiten B: Shiroishi Industry Co., Ltd., fine-grained calcium carbonate, average particle size 3.6 μm

In each of Examples 1, 2, 3, and 4, the ejection of the plastigel from the ejection nozzle is smooth, the cross-sectional shape maintains a predetermined shape, and the shape changes even after heating. It was possible to obtain a window glass with a gasket, which has a satisfactory appearance and strength. In addition, in Examples 2 and 3, the gaskets having a strong adhesion to the glass and could not be easily peeled were obtained. In Comparative Example 3, the plastigel was smoothly discharged from the discharge mouthpiece, but the desired shape could not be maintained and the plastigel immediately flowed out. In Comparative Example 4, the maximum thickness was deformed. Comparative Example 4 could not be discharged.

[0025]

EFFECTS OF THE INVENTION By using the plastigel of the present invention, a burr-free molded product can be easily and accurately manufactured by a simple shape of the discharge mouth under normal temperature and pressure without using an expensive mold and a high-pressure injection device. be able to. Also, since it is pushed out at normal pressure, it is not necessary to increase the tightening force of the mounted object, for example, the window glass at the time of molding, so not only can these damages be prevented, but it is very easy to add a gasket to a large glass. There are also advantages. Further, it eliminates the drawbacks of the conventional plastigel, such as the fact that there is no entrapment of air and a molded product with a thin wall thickness can be easily manufactured.

[0026]

[Brief description of drawings]

FIG. 1 is an explanatory view showing an example of a method for manufacturing a window glass with a gasket of the present invention.

[0027]

FIG. 2 is a cross-sectional view of an example of a method for manufacturing a window glass with a gasket according to the present invention.

[0028]

[Explanation of symbols]

 1 Glass 2 Discharged plastigel 3 Discharge mouth of gun 4 Plastigel supply hose a Maximum thickness in vertical direction of glass surface b Horizontal width in glass surface

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[Procedure amendment]

[Submission date] May 14, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

<Viscosity> The viscosity at a shear rate of 1 sec _-1 and a shear rate of 100 sec ^-1 was measured using a Rotovisco rotational viscometer. Control console: HAAKE ROTOVIS
CO RV-3 sensor: cone plate type PK-1-3 ° <melt viscosity> Using Rheometrics Dynamic Spectrometer (manufactured by Rheometrics) and parallel plate 40 mmφ, frequency 0.25H
z, plate gap 3 mm, heating rate 10 ° C /
The melt viscosity of the composition was measured under the conditions of a minute and a measurement temperature of 180 ° C. The evaluation results are shown in Table 1.

Claims (3)

[Claims] 1. 100 parts by weight of a vinyl chloride resin having an average single particle size of 5 μm or less and 20 to 100 parts by weight of a filler having an average single particle size of 0.5 μm or less among 40 to 80 parts by weight of a plasticizer. Plastigel dispersed in water and has a viscosity at room temperature of 500,000 cps to 5,000,000 cps at a shear rate of 1 sec ^-1 .
Hereinafter, a plastigel composition having a viscosity of 500,000 cps or less at a shear rate of 100 sec ^-1 , and having a melt viscosity at 180 ° C of 100,000 cps or more. 2. A vinyl chloride copolymer containing not more than 2.5 to 50% by weight of a polar group-containing vinyl monomer unit as all or part of the vinyl chloride resin component.
The described plastigel composition. 3. A molded article obtained by heating and melting a molded article obtained by extruding the composition according to claim 1 or 2 from a die under normal temperature and normal pressure.