JPH05262949A - Plastigel composition and molded body using the same composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, having a prescribed viscosity, excellent in fluidity, moldability, appearance and strength and useful as window glass with gaskets, etc., by dispersing a specific copolymer, a specified swollen resin, a specific plasticizer and a specified filler in a specific proportion. CONSTITUTION:The objective composition is composed of a plastigel prepared by dispersing (A) 100 pts.wt. acrylic acid ester-based copolymer having main constituent units composed of (i) 98-50wt.% alkyl (meth)acrylate unit having a 1-8C alkyl group and (ii) 2-50wt.% diene-based monomer unit and having <=5mum average single particle diameter, (B) 5-100 pts.wt. swollen resin prepared by making a plasticizer such as a phthalic acid ester-based plasticizer absorbed in an amount of 0.3-3 times based on the resin in the component (A) and (C) 40-80 pts.wt. plasticizer in (D) 20-150 pts.wt. filler having $0.5mum average single particle diameter. This composition has 500000-5000000cP viscosity at 1sec<-1> shearing rate and <=500000cP viscosity at 100sec<-1> shearing rate respectively at 15 deg.C. Furthermore, a molding obtained by extruding this composition under ordinary pressure is molded and thermally melted to afford the objective molded body.

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 producing a soft molded article having a part and the like, and a molded article produced using the same.

[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, there is a problem that the gasket has a bad appearance such as wrinkles when used in a bent part and is difficult to install. there were. 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, a method of manufacturing the window glass with a gasket, which is taken out from the mold and integrated with the gasket material at the peripheral edge of the glass, has been proposed. However, in this method, since the synthetic resin or rubber is injected in a melted and highly viscous state, the gasket material has the 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. Especially when the window glass is bent, it is difficult to make the curvature of the glass uniform,
Therefore, when the mold is tightened, there are many places where stress is intensively applied, which often leads to breakage. 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, a 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). This method
A method in which a window glass is placed in a molding die, a gasket molding cavity space 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 and then heated and solidified. Is. 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 tightened tightly, gel may penetrate into the gap and cause burr, and since the plastigel is injected into the sealed mold at low pressure, air bubbles There is a risk that it will be molded in a state where the
There is a concern that the strength of the product after it becomes a product may deteriorate.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a plastigel which can easily prevent the formation of burrs and can be accurately molded into an arbitrary shape in the above molding method.

[0004]

DISCLOSURE OF THE INVENTION The present inventors believe that the drawbacks of the plastigel depend on the viscoelastic properties of the plastigel. First, the plastigel having a high viscosity that is hardly deformed by its own weight in a short time is selected. 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. The phenomenon that the plasticizer that contributes to the fluidity decreases and the viscosity increases by the same principle when swelling the plasticizer in the acrylic ester copolymer is used to increase the viscosity of the plastigel. If the high viscosity behavior of plastigel is controlled by selecting the compounding amount of compounded particles, the particle size and the swelling degree of the plasticizer, the problems of burr formation and bubbles can be solved. The present invention has been completed based on this finding have found to be able to.

That is, in the present invention, the main constitutional unit is (a)
98 to 50% by weight of an alkyl acrylate unit and / or methacrylic acid alkyl ester unit having an alkyl group having 1 to 8 carbon atoms and (b) a diene monomer unit 2 to 50
And 100% by weight of an acrylic acid ester-based copolymer (A) having an average single particle size of 5 μm or less, and an acrylic acid ester-based copolymer having an average single particle size of 5 μm or more of the resin. 5 to 100 parts by weight of a swelling resin (B) having absorbed 0.3 to 3 times the weight of the plasticizer, and 40 to 8 of the plasticizer (C).
0 part by weight and 20 to 150 parts by weight of a filler (D) having an average single particle size of 0.5 μm or less are dispersed, and the viscosity at 15 ° C. is 500,000 cps or more and 5 million cps at a shear rate of 1 sec ^−1.
The present invention provides a plastigel composition having a viscosity of 500,000 cps or less at a shear rate of 100 sec ^-1 , and a molded product obtained by extruding the composition under normal pressure and heating and melting. The viscosity at 15 ° C. indicates that the plastigel used in the present invention is a highly viscous composition that does not flow-deform under its own weight when left for a short time at room temperature.

The plastigel of the present invention is characterized in that an acrylic acid ester type copolymer having absorbed a plasticizer and an acrylic acid ester type copolymer not having absorbed the plasticizer are used in combination. The former contributes to increasing the viscosity of plastigel by absorption, and the latter contributes to increasing the viscosity by reducing the particle size. In the composition of the present invention, the copolymer particles used as the component (A) have the following main components:
An acrylic acid alkyl ester or a methacrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms and a diene monomer are copolymerized with each other, and the acrylic acid alkyl ester or the methacrylic acid alkyl ester is used. As, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth). Acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate and the like can be mentioned, and one of these alone or Combine two or more It is possible to use Te Align.

On the other hand, examples of the diene-based monomer include conjugated diene-based compounds such as butadiene, isoprene, 1,3-pentadiene, cyclopentadiene and dicyclopentadiene, and non-conjugated dienes such as 1,4-hexadiene and ethylidene norbornene. Examples thereof include system compounds, and these can be used alone or in combination of two or more. Of these, butadiene and isoprene are particularly preferable. In the copolymer of the present invention, the content ratio of the (a) monomer unit and the (b) monomer unit is 98 to 50% by weight of the (a) monomer unit based on the total amount thereof, preferably 95 to 70% by weight of (b) monomer units 2 to 5
0% by weight, preferably 5 to 30% by weight is used. When the content of the monomer unit (b) is less than 2% by weight, the sheet obtained by mixing with a plasticizer such as di-2-ethylhexyl phthalate and heat-molding is difficult to be plasticized, and bleeding is remarkable. Further, if it is 5% by weight or more, a whitening phenomenon does not occur during stretching of the molded sheet, which is desirable. On the other hand, the content of the monomer unit (b) is 5
If it exceeds 0% by weight, there is no moldability and it becomes impractical. Further, when the content of the monomer unit (b) is 30% by weight or less, the softening temperature of the copolymer particles gradually increases, and spray drying becomes easy, so coagulation drying becomes unnecessary, and as a result, the plastisol viscosity It is desirable because it lowers the physical properties of the sheet and improves the physical properties of the sheet. Therefore, when the contents of the (a) monomer unit and the (b) monomer unit are in the ranges of 95 to 70% by weight and 5 to 30% by weight, respectively, plastisol has stable viscosity characteristics and physical properties. It is particularly desirable because it will be

If desired, the copolymer may contain other monomer units copolymerizable with the above-mentioned monomer, within the range not impairing the object of the present invention. In this case, the content of the other monomer unit is usually selected so as to be 10% by weight or less in the copolymer. Examples of the other copolymerizable monomer include, for example, a functional group-containing unsaturated monomer for improving the adhesiveness of the plastisol composition, specifically, glycidyl (meth) acrylate, 3,4-epoxy. A polymerizable unsaturated compound having an epoxy group such as cyclohexylmethyl (meth) acrylate and cyclohexene monoxide, a carboxyl group such as acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid and their acid anhydrides. Polymerizable unsaturated compound having, 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 2-aminobutyl (meth) acrylate,
3-aminobutyl (meth) acrylate, 4-aminobutyl (meth) acrylate, (meth) acrylamide,
N-2-aminoethyl (meth) acrylamide, N-2
-Amino group-containing polymerizable unsaturated compounds such as aminopropyl (meth) acrylamide and N-3-aminopropyl (meth) acrylamide, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-
Examples thereof include hydroxyl group-containing polymerizable unsaturated compounds such as hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These functional group-containing unsaturated monomers may be used alone or in combination of two or more.

In the present invention, the copolymer of the component (A) is preferably produced by an emulsion polymerization method or a seeded emulsion polymerization method which is commonly used in the production of a paste processing resin. When a polymer having a relatively large particle size to be blended for the purpose of reducing the sol viscosity or matting the surface of a molded product is required, the suspension polymerization method or the bulk polymerization method is suitable. In the emulsion polymerization method, in an aqueous medium containing an emulsifier and a polymerization initiator, a (meth) acrylic acid alkyl ester is copolymerized with a diene monomer and optionally a functional group-containing unsaturated monomer. Is the way. As the emulsifier, an anionic surfactant or a combination thereof with a nonionic surfactant is usually used. As the anionic surfactant, known ones usually used in emulsion polymerization, for example, alkylbenzene sulfonate, alkyl sulfonate, alkyl sulfate ester salt, fatty acid metal salt, polyoxyalkyl ether sulfate ester salt, polyoxyethylene carboxylic acid salt are used. Examples thereof include acid ester sulfate ester salts, polyoxyethylene alkylphenyl ether sulfate ester salts, and succinic acid dialkyl ester sulfonates, and these can be used alone or in combination of two or more.

As the nonionic surfactant, for example, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether glycerin borate ester, A compound having a polyoxyethylene chain in the molecule, such as polyoxyethylene alkyl ether phosphate, polyoxyethylene, etc., and having a surfactant activity, and the polyoxyethylene chain of the compound is a copolymer of oxyethylene and oxypropylene. Substituted compounds include sorbitan fatty acid ester, fatty acid glycerin ester, glycerin fatty acid ester, pentaerythritol fatty acid ester, etc. It can be used in combination or species. Regarding the amount of these surfactants used, the anionic surfactant is usually selected in the range of 0.1 to 5 parts by weight per 100 parts by weight of the monomer used, and the nonionic surfactant is usually It is selected in the range of 0.1 to 5 parts by weight.

On the other hand, as the polymerization initiator, a water-soluble inorganic peroxide or a combination of a water-soluble reducing agent and an organic peroxide is used. Examples of the water-soluble inorganic peroxide include potassium persulfate and ammonium persulfate. As the water-soluble reducing agent, for example, a reducing agent used as an ordinary radical redox polymerization catalyst component soluble in water, for example, ethylenediaminetetraacetic acid or its sodium salt or potassium salt, or a heavy metal such as iron, copper, or chromium. Complex compound with, sulfinic acid or its sodium salt or potassium salt, L-ascorbic acid or its sodium salt, potassium salt, calcium salt, ferrous pyrophosphate, ferrous sulfate, ferrous ammonium sulfate, sodium sulfite, Examples thereof include sodium acid sulfite, sodium formaldehyde sulfoxylate, and reducing sugars, and these may be used alone or in combination of two or more. The amount of these reducing agents used is usually selected from the range of 0.0001 to 5 parts by weight per 100 parts by weight of the monomers used. Examples of the organic peroxide include cumene hydroperoxide, p-cymene hydroperoxide, t-
Butyl isopropyl benzene hydroperoxide, diisopropyl benzene hydroperoxide, p-menthane hydroperoxide, decalin hydroperoxide, t
And hydroperoxides such as amyl hydroperoxide, t-butyl hydroperoxide, isopropyl hydroperoxide. These organic peroxides may be used alone or in combination of two or more. The amount to be used is selected in the range of 0.001 to 5 parts by weight per 100 parts by weight of the monomer usually used.

In this emulsion polymerization, higher fatty acids, higher alcohols, inorganic salts, water-soluble polymer compounds and the like may be used in combination in order to promote the action of the emulsifier and the polymerization catalyst used. In this emulsion polymerization, usually 3
Polymerization is carried out at a temperature in the range of 0 to 80 ° C. In this way, a latex in which copolymer fine particles having a particle size of about 0.03 to 0.7 μm are uniformly dispersed can be obtained. This latex is usually subjected to a known treatment such as salting out or spray drying, and the polymer is taken out as a solid. The molecular weight of the polymer is appropriately adjusted by the reaction temperature and the molecular weight modifier according to the purpose. On the other hand, the seeded emulsion polymerization method is based on the resin particles prepared by the emulsion polymerization method as a core, and the emulsifier and the water-soluble inorganic peroxide which are the anionic surfactant or a combination of the anionic surfactant and the nonionic surfactant. Alternatively, it is a method in which a polymerization initiator comprising a combination of the water-soluble reducing agent and an organic peroxide is used to carry out a particle enlargement polymerization reaction in an aqueous medium. The diameter of the core particles used in this case is usually in the range of 0.03 to 0.7 μm on average, and the amount used is usually 1 per 100 parts by weight of the monomer used.
It is selected in the range of 50 parts by weight. The amounts of the emulsifier and the polymerization initiator used are the same as in the emulsion polymerization method.

Next, a preferred example of the seeded emulsion polymerization method will be described. First, an aqueous emulsion of desired resin core particles is prepared, and then the water-soluble reducing agent and the monomer are charged and heated. And maintain the temperature at about 30 to 80 ° C. On the other hand, an aqueous emulsion of organic peroxide and an aqueous solution of the emulsifier are separately prepared by using the emulsifier, and these are usually added to an aqueous emulsion containing the resin core particles, a water-soluble reducing agent and a monomer. The polymerization reaction is carried out by continuously charging while maintaining the temperature in the range of 30 to 80 ° C.
In this seed emulsion polymerization, higher fatty acids, higher alcohols, inorganic salts, water-soluble polymer compounds and the like may be used in combination in order to promote the action of the emulsifier and the polymerization catalyst used. After the completion of the polymerization reaction, from the emulsion thus obtained containing the copolymer particles having an average particle size of 0.3 to 2 μm, the copolymer is converted into a solid matter in the same manner as in the case of the emulsion polymerization. Take it out. The molecular weight of this copolymer is appropriately adjusted by the reaction temperature, the molecular weight modifier and the like depending on the purpose.

The swelling resin (B) in which the second resin component used in the plastigel of the present invention absorbs a plasticizer can stir an acrylic acid ester-based copolymer of 5 μm or more while heating with a ribbon mixer, a Henschel, a kneader or the like. Put in an apparatus and heat to a temperature above the temperature at which the acrylic acid ester-based copolymer absorbs the plasticizer to absorb, for example, 30 to 300 parts by weight of the plasticizer with respect to 100 parts by weight of the acrylic acid ester-based copolymer. To obtain a powder. However,
When an acrylic acid ester-based copolymer having an average single particle size of less than 5 μm is used, it takes a long time to absorb the plasticizer, or when the absorption is completed, it gels and becomes a block, which is similar to a powder. It becomes difficult to disperse in plastigel. Therefore, selecting the particle size of the acrylic acid ester-based copolymer that swells the plasticizer to 5 μm or more is an essential condition for obtaining a high-viscosity plastigel by the swelling method. The plastigel of the present invention is a method of increasing the viscosity by swelling the plasticizer in a part of the acrylic ester-based copolymer used in this way, and improving the viscosity by making the particle size of the filler particles very small. By synergy,
It has achieved high viscosity of plastigel.

In the composition of the present invention, a plasticizer is used as the component (C). The plasticizer is not particularly limited, and those conventionally used as plasticizers for vinyl chloride resin plastisols, such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di- (2-ethylhexyl) phthalate, di-n-octyl phthalate. , Diisobutyl phthalate, diheptyl phthalate,
Diphenylphthalate, diisodecylphthalate, ditridecylphthalate, diundecylphthalate, di (heptyl, nonyl, undecyl) phthalate, benzylphthalate, butylbenzylphthalate, dinonylphthalate, dicyclohexylphthalate and other phthalic acid derivatives, dimethylisophthalate, di- ( 2-Ethylhexyl) isophthalate, isophthalic acid derivative such as diisooctyl isophthalate, di- (2-ethylhexyl)
Tetrahydrophthalate, di-n-octyltetrahydrophthalate, tetrahydrophthalic acid derivatives such as diisodecyltetrahydrophthalate, di-n-butyl adipate, di- (2-ethylhexyl) adipate, diisodecyl adipate, adipic acid derivatives such as diisononyl adipate, di- Azelaic acid derivatives such as (2-ethylhexyl) azelate, diisooctyl azelate and di-n-hexyl azelate, sebacic acid derivatives such as di-n-butyl sebacate and di- (2-ethylhexyl) sebacate, di-n- Butyl maleate, dimethyl maleate, diethyl maleate, maleic acid derivatives such as di- (2-ethylhexyl) malate, di-n-butyl fumarate, fumaric acid derivatives such as di- (2-ethylhexyl) fumarate, -(2-Ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisodecyl trimellitate, triisooctyl trimellitate, tri-n-hexyl trimellitate, triisononyl trimellitate, etc. Acid derivative,
Pyromellitic acid derivatives such as tetra- (2-ethylhexyl) pyromellitate and tetra-n-octylpyromellitate, triethyl citrate, tri-n-butyl citrate, acetyltriethyl citrate, acetyltri- (2-ethylhexyl) citrate Itaconic acid derivatives such as citric acid derivatives, monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, di- (2-ethylhexyl) itaconate, butyl oleate, glyceryl monooleate, diethylene glycol mono Oleate and other oleic acid derivatives, methyl acetyl ricinoleate, butyl acetyl ricinoleate, glyceryl monoricinoleate, diethylene glycol monoricinoleate and other ricinoleic acid derivatives , Stearic acid derivatives such as n-butyl stearate, glycerin monostearate, diethylene glycol distearate, other fatty acid derivatives such as diethylene glycol monolaurate, diethylene glycol dipelargonate, pentaerythritol fatty acid ester, triethyl phosphate, tributyl phosphate, tributyl phosphate. Phosphoric acid derivatives such as-(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (chloroethyl) phosphate, diethylene glycol dibenzoate, dipropylene glycol Dibenzoate, triethylene glycol dibenzoate, triethylene glycol Ruji -
(2-ethylbutyrate), triethylene glycol di- (2-ethylhexoate), glycol derivative such as dibutylmethylene bisthioglycolate, glycerol monoacetate, glycerol triacetate, glycerol derivative such as glycerol tributyrate, epoxy Soybean oil, epoxy butyl stearate, epoxy hexahydrophthalic acid di-2-ethylhexyl, epoxy hexahydrophthalic acid diisodecyl, epoxy triglyceride, epoxidized octyl oleate, epoxy derivative such as epoxidized decyl oleate, adipic acid polyester Polyester plasticizer such as sebacic acid polyester, phthalic acid polyester, partially hydrogenated terphenyl, adhesive plasticizer, diallyl phthalate, acetic acid Although such polymeric plasticizers such as Le monomer or oligomer can be cited, it is preferred that the phthalate in these. One of these plasticizers
These may be used alone or in combination of two or more. Further, a plasticizer in which a high molecular compound such as rubber or resin is dissolved may be optionally used.

The filler (D) used in the present invention is calcium carbonate, mica, talc, kaolin clay, celite,
Asbestos, perlite, baryta, silica, silica sand, flake graphite, dolomite limestone, gypsum, fine aluminum powder, anhydrous silicic acid, fine particles of inorganic substances such as calcium carbonate,
Organic / inorganic composite thixotropic agents, organic thixotropic agents, etc. are mentioned.Thixotropic agents include silicic acid anhydride, silicic acid type such as hydrous silicic acid, bentonite type such as organic bentonite, asbestos type such as silodex, and dibenzylidene sorbitol. Organic materials and the like can be used, and all materials used by adding them to the composition of the polyvinyl chloride resin and the plasticizer can be used. A filler having an average single particle size of 0.5 μm or less is essential for the present invention. For example, when the high viscosity required for the plastigel of the present invention is obtained by other conditions, the average single particle size is 50 or more fillers of the same kind or other kinds whose particle size exceeds 0.5 μm
It can be replaced within the range of not more than wt%. 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
sec ^-1 above 500,000 cps and below 5 million cps, especially 1 million cs
In order to obtain ps or more, 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 plastigel of the present invention includes a diluent, a stabilizer, a pigment,
A compounding agent that can be usually used for processing polyvinyl chloride, such as an ultraviolet absorber, can be appropriately used, and this also changes the viscosity. In the plastigel of the present invention, high viscosity is achieved by the two kinds of acrylic acid ester-based copolymers used as essential components and the filler, but the mixing ratio of each is the average single particle size of the resin. The amount of the three components can be selected so that the plastigel of the present invention falls within a specific high viscosity range, depending on the types and amounts of the filler and the plasticizer.

The plastigel of the present invention has an average single particle size of 5
With respect to 100 parts by weight of an acrylic acid ester-based copolymer having a size of not more than μm, an acrylic acid ester-based copolymer having an average single particle size of 5 μm or more is allowed to absorb 0.3 to 3 times the weight of the plasticizer of the resin. Further, 5 to 100 parts by weight of the swelling resin and 20 to 150 parts by weight of the filler having an average single particle size of 0.5 μm or less are dispersed in 40 to 80 parts by weight of the plasticizer. If the amount of the swollen acrylic acid ester-based copolymer component is less than 5 parts by weight in this mixing ratio, the hardness of the molded article will be too high, and the hardness will be 100%.
If it exceeds the weight part, the surface of the molded product becomes rough and the appearance deteriorates. In this blending ratio, the proportion of the filler is 20
If it is less than 1 part by weight, the viscosity of plastigel is low,
If the amount is more than the weight part, thixotropy is deteriorated, and the shape of the shaped gel is easily broken. Further, if the proportion of the plasticizer is less than 40 parts by weight, the molded article becomes hard, and if it exceeds 80 parts by weight, the viscosity of the plastigel decreases.

The plastigel of the present invention has a viscosity at room temperature of at least 500,000 cps 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: 50 at a shear rate of 1 sec ^-1
If it is less than 10,000 cps, there is a risk that it will flow and flow out from the open part when it comes out of the mold. Meanwhile, 5
If it is more than, 000,000 cps, the fluidity is poor and extrusion molding becomes difficult under normal pressure. At a shear rate of 100 sec ^-1 , 5
If it is more than 0,000 cps, the supply pipe resistance is large, and the supply pressure must be increased, which makes it impossible to perform the easy molding which is the object of the present invention, and also the dischargeability is inferior and an arbitrary shape is obtained. Becomes difficult to manufacture. It is possible to produce the plastigel of the present invention by combining the respective components of the plastigel as described above and mixing and agitating them with a known mixer such as an existing planetary mixer, kneader or roll. The plastigel of the present invention can be extruded at room temperature and melted by heating to form a molded product easily.

For example, a gasket can be formed and attached to the peripheral portion of the glass by an extruder as shown in FIG. When forming on the entire peripheral edge of the glass, the discharge start part and discharge end part are discontinuous, but since the plastigel before heat treatment can easily repair and shape the shape, it is easy to form a continuous curved surface with a spatula etc. Can be modified. After the plastigel of the present invention is attached to the peripheral portion of the window glass, the plastigel is melted by heating, and the strength can be increased by cooling to room temperature. The heating method can be used without particular limitation 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. Furthermore, the plastigel of the present invention preferably has adhesiveness to glass or the like that is formed by contact with the plastigel.

As a method for imparting adhesiveness to the plastigel of the present invention, application of a primer to the surface of glass can be mentioned. 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, and epoxy resin. 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 can be evaluated by a 90 ° peel test. In the present invention, the adhesive strength is preferably 1 kg / cm (tensile strength 200 mm / min) or more, and particularly 3 kg / cm or more.

[0022]

EXAMPLES The present invention will be described in more detail with reference to the following examples. Examples 1-3, Comparative Examples 1-4 Methyl methacrylate 95% by weight and butadiene 5% by weight
100 parts by weight of a resin powder having an average particle size of 40 μm obtained by emulsion polymerization and 100 parts by weight of diisodecyl phthalate are placed in a ribbon mixer and heated at 100 ° C. for 20 minutes while mixing to obtain a composition of the present invention. A plasticizer-absorbing acrylic acid ester copolymer resin powder corresponding to the component (B) was prepared and used in the examples. Next, as a component A resin powder, methyl methacrylate 90 was obtained by emulsion polymerization.
A resin powder of a copolymer (average particle diameter 0.1 μm) of 10% by weight of butadiene and 0.1% by weight of butadiene is produced, and further, 65% by weight of methyl methacrylate, 20% by weight of ethyl acrylate, 10% by weight of isoprene, glycidyl methacrylate by emulsion polymerization. 5% by weight of copolymer (average particle size 0.3μ
m) resin powder was produced. The resin powder or the resin powder and other components were sampled in the plasticizer-absorbing resin powder in the amounts shown in Table 1, mixed in a Hobart mixer, and defoamed to prepare a plastigel. Each of the obtained plastigel was applied onto two glass plates so as to have a coating thickness of 3 mm and a coating width of 150 mm × 100 mm, and heated in a hot air circulation oven at 140 ° C. for 10 minutes. Various physical properties were measured and evaluated using the sheet thus obtained. The methods for measuring and evaluating physical properties in Examples and Comparative Examples are as follows.

<Hardness> The sample is 50 mm × 100 mm
The sheet was cut into three sheets, the three sheets were overlaid, and the hardness was measured by a spring type hardness test (A type). (JIS
Based on K-6301. ) <Shape after heating> Fig. 1 shows an apparatus for directly discharging plastigel to the peripheral edge of the glass according to the present invention, and plastigel is adhered to the peripheral edge of the glass while discharging the plastigel from a gun mouthpiece having a predetermined shape. It is a perspective view showing a state. 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, and discharge from a hose 4 having an inner diameter of 10 mmφ at 50 cc / min from a gun discharge mouthpiece 3, 30 cm × 50 cm × 3 m
A gel having a maximum thickness of 20 mm in the vertical direction of the glass surface and a width of 10 mm in the horizontal direction was attached while moving to the peripheral portion of the m-thick glass, and heated in a hot air oven at 140 ° C. for 15 minutes. Then, the temperature was cooled to near room temperature, and the shape after heating was visually evaluated. <Viscosity> Using a Rotovisco rotary viscometer, shear rate 1 sec
^-1 and a shear rate of 100 sec ^-1 were measured. Control console: HAAKE ROTOVIS
CO RV-3 sensor: cone-plate type PK-1-3 ° Table 1 shows the evaluation results.

[0024]

[Table 1]

Note 1) Zeon resin 43F: vinyl chloride resin manufactured by Nippon Zeon Co., Ltd., average particle size: 0.2 μm 2) Epoxy resin: bisphenol A manufactured by Asahi Denka Co., Ltd.
Epoxy resin E-4001 3) Polyethyleneimine: Polyethyleneimine SP-018 manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd. 4) Calseeds PL: Fine calcium carbonate manufactured by Kamijima Chemical Co., Ltd., average particle size 0.1 μm 5) Whiten B: Shiroishi Industry Co., Ltd., fine-grained calcium carbonate, average particle size 3.6 μm

In each of Examples 1, 2, and 3, the ejection of the plastigel from the ejection mouthpiece was smooth, the cross-sectional shape maintained a predetermined shape, and the shape did not change even after heating, and the appearance was improved. It was possible to obtain a window glass with a gasket having satisfactory strength. In particular, in Example 2, the gasket was firmly adhered to the glass and could not be easily peeled off.

In Comparative Example 1, the hardness of the molded product was too large and it was not suitable as a gasket. In Comparative Example 2, the viscosity of the plastigel was too high to allow ejection. In Comparative Example 3, the viscosity of the plastigel was too low, and the gasket shape immediately collapsed after discharging. In Comparative Example 4, the molded product had a small tensile strength and was brittle.

[0028]

EFFECTS OF THE INVENTION By using the plastigel of the present invention, a burr-free molded product can be easily formed by extrusion molding under normal pressure without using an expensive mold and a high-pressure injection device, due to the simple shape of the discharge nozzle. Can be manufactured accurately. Further, since the molding is performed under normal pressure, not only can the window glass to which the gasket is attached be prevented from being damaged, but also the gasket can be easily added to a large glass.

[Brief description of drawings]

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

[Explanation of symbols]

 1 Glass 2 Discharged Plastigel 3 Gun Discharge Port 4 Plastigel Supply Hose

Claims (3)

[Claims] 1. A main constituent unit is (a) an alkyl acrylate unit and / or a methacrylic acid alkyl ester unit in which the alkyl group has 1 to 8 carbon atoms, and 98 to 50% by weight, and (b) a diene monomer unit. 100 parts by weight of an acrylic acid ester-based copolymer (A) having an average single particle diameter of 5 μm or less and 2 to 50% by weight, and the acrylic acid ester-based copolymer having an average single particle diameter of 5 μm or more. From 0.3 of the resin
Swelling resin (B) 5-10 having absorbed 3 times the weight of plasticizer
0 parts by weight, 40 to 80 parts by weight of the plasticizer (C), and 20 to 150 parts by weight of the filler (D) having an average single particle size of 0.5 μm or less.
A plastigel composition obtained by dispersing parts by weight, which has a viscosity at 15 ° C. of not less than 500,000 cps and not more than 5 million cps at a shear rate of 1 sec ⁻¹ and not more than 500,000 cps at a shear rate of 100 sec ⁻¹ . .. 2. The plastigel composition according to claim 1, wherein the plasticizer contains at least a phthalate ester plasticizer. 3. A molded product obtained by extruding the composition according to claim 1 or 2 under normal pressure, and heating and melting the composition.