JPH05262947A - Plastigel composition and molded body using the same composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, composed of a specific acrylic acid ester-based copolymer, a specified plasticizer and a specific filler in a specified proportion, having a prescribed viscosity, excellent in fluidity, moldability, appearance and strength and useful as window glass with gaskets, etc. 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 and (B) 40-80 pts.wt. plasticizer such as a phthalic acid ester-based plasticizer in (C) 20-150 pts.wt. filler such as calcium carbonate having $0.5mum average single particle diameter. This plastigel has 500000-5000000cP viscosity at 1sec<-1> shearing rate and <=500000cP viscosity at 100sec<-1> shearing rate respectively at ordinary temperature. Furthermore, a molding obtained by extruding this composition through a nozzle at ordinary temperature under ordinary pressure is 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 manufacturing a flexible molded product having a shape having a portion.

[0002]

2. Description of the Related Art Conventionally, it has been widely practiced to attach a gasket made of synthetic resin or rubber to the periphery of window glass for automobiles for the purpose of sealing or decoration. This gasket is molded by a method such as melt extrusion, but since the molded product is string-shaped, if the curve of the mounting part has a large bend, the gasket wrinkles and the appearance deteriorates, However, there was a problem that it was difficult and very time-consuming. To solve this problem, for example,
An automobile window glass is placed in a molding die with a space formed at its peripheral edge, and a gasket material such as synthetic resin or rubber is injected in the above-mentioned space in a molten state, cooled, and then taken out from the mold to obtain the glass peripheral edge. There has been proposed a method of manufacturing a window glass with a gasket, which is integrated with a gasket material in a portion.
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, stress may be 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, 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). 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 solidifying by heating.
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. Also, for example, the cross-sectional shape of the gasket is 0.5 to
In the case of having a thin wall portion of about 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. 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. 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, in the present invention, the main constituent unit (A) having an average single particle size of 5 μm or less is (a) the alkyl group has 1 to 8 carbon atoms.
100 parts by weight of an acrylic acid ester-based copolymer comprising 98 to 50% by weight of an alkyl acrylate unit and / or an alkyl methacrylic acid unit of (2) and 2 to 50% by weight of a diene monomer unit (b). ) Plasticizer 40-
A plastigel having 80 parts by weight and 20 to 150 parts by weight of a filler (C) having an average single particle size of 0.5 μm or less, and having a viscosity at room temperature of 500,000 cps or more at a shear rate of 1 sec ⁻¹ . 5 million cps or less, shear rate 100 sec
^-1 provides a plastigel composition having a viscosity of 500,000 cps or less.

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 acrylic acid ester-based copolymer having an average single particle size of 5 μm or less used in the present invention is an acrylic acid ester-based copolymer homopolymer or a copolymer with 50% by weight or less of another monomer,
The average primary particle size obtained by emulsion polymerization or fine suspension polymerization is 5
It is a fine particle polymer having a particle size of not more than μm and is used for plastisol or plastigel processing.

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

When the acrylic acid ester-based copolymer having an average single particle size of more than 5 μm is 50% by weight or more, the viscosity at room temperature is 500,000 cps or more and 5,000,000 cps at a shear rate of 1 sec ^-1.
A large amount of filler or the like must be used in order to set the range to cps or less, particularly to 1,000,000 cps or more, and such a high viscosity is not obtained, and as a result, the hardness is increased and the physical properties are deteriorated. The acrylic acid ester-based copolymer having an average single particle size of 5 μm or less used in the present invention is a concept including an aggregate of particles having an average single particle size of 5 μm or less, and this aggregate is also preferably used in the present invention. Can be used for As a method of coagulating the acrylate copolymer, a method of spraying the polymerized latex by coagulating it by breaking the stability of the latex with acid, salt, electrolysis (electricity), centrifugation, floating, dialysis, heat, or spraying There is a method of agglomerating into particles by drying.

The copolymer particles used as the component (A) in the composition of the present invention include, as main components, an alkyl acrylate or alkyl methacrylate having an alkyl group having 1 to 8 carbon atoms and a diene monomer. And an acrylic acid alkyl ester or a methacrylic acid alkyl ester, 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) ac Rate, etc. n- octyl (meth) acrylate and the like, which may be used in combination of at least one kind alone or in combination.

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 may be used alone or in combination of two or more, and among these, butadiene and isoprene are particularly preferable. In the copolymer, the content ratio of the unit formed from the (a) unit of the (meth) acrylic acid alkyl ester and the unit formed from the (b) unit of the diene monomer is the total amount of them. Based on the above, it is necessary that the amount of the (a) unit is in the range of 98 to 50% by weight, preferably 95 to 70% by weight, and the amount of the (b) unit is in the range of 2 to 50% by weight, preferably 5 to 30% by weight.

When the content of the unit (b) is less than 2% by weight, a 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, in the range of 2 to 5% by weight, the whitening phenomenon may occur when the molded sheet is stretched. On the other hand, the content of the (b) unit is 30
If it exceeds 5% by weight, the softening temperature of the copolymer particles becomes low and spray drying becomes difficult, so coagulation drying becomes necessary, resulting in an increase in plastisol viscosity and a deterioration in sheet properties, which is not preferable. If the content of the unit (b) exceeds 50% by weight, it becomes completely impractical. In particular, the contents of the (a) unit and the (b) unit are each 95-
When it is in the range of 70% by weight and 5 to 30% by weight, the plastisol has stable viscosity characteristics and physical properties.

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, but the sol viscosity is reduced or When a material having a relatively large particle size to be blended for the purpose of matting the surface of a molded article is required, the suspension polymerization method or the bulk polymerization method is advantageous. 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. Acid ester sulfate ester salt,
Examples thereof include polyoxyethylene alkylphenyl ether sulfuric acid 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 sodium salt or potassium salt thereof, L-ascorbic acid or sodium salt thereof, potassium salt, calcium salt, ferrous pyrophosphate, ferrous sulfate, ferrous ammonium sulfate, sodium sulfite, Examples thereof include sodium acid sulfite, sodium formaldehyde sulfoxylate, reducing sugars and the like, and these can 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 peroxides include cumene hydroperoxide, p-cymene hydroperoxide, t-butyl isopropylbenzene hydroperoxide, diisopropylbenzene hydroperoxide and p-.
Mentioned are hydroperoxides such as menthane hydroperoxide, decalin hydroperoxide, t-amyl hydroperoxide, t-butyl hydroperoxide and isopropyl hydroperoxide. These organic peroxides may be used alone or in combination of two or more. The amount of the monomer used is 10
It is selected in the range of 0.001 to 5 parts by weight per 0 parts by weight. 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 30 to 80
The polymerization is carried out at temperatures in the range of ° 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,
The polymer is removed 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 selected in the range of 1 to 50 parts by weight per 100 parts by weight of the monomer used. . 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 can 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 can be appropriately adjusted by a reaction temperature, a molecular weight modifier or the like depending on the purpose.

In the composition of the present invention, a plasticizer is used as the component (B). The plasticizer is not particularly limited, and is conventionally used as a plasticizer 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, di- (2-ethylhexyl) maleate and other maleic acid derivatives, di-n-butyl fumarate, di- (2-ethylhexyl) fumarate and other fumaric acid derivatives , Tri- (2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisodecyl trimellitate, triisooctyl trimellitate, tri-n-hexyl trimellitate, triisononyl trimellitate, etc. Trimellitic acid derivative,
Pyromellitic acid derivatives such as tetra- (2-ethylhexyl) pyromellitate and tetra-n-octylpyromellitate, triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri- (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 Oleic acid derivatives such as oleate, methylacetylricinoleate, butylacetylricinoleate, glyceryl monoricinoleate, diethylene glycol monoricinoleate and other ricinoleic acid Conductors, 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, Phosphoric acid derivatives such as tri- (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 di -
(2-Ethylbutyrate), triethylene glycol di- (2-ethylhexoate), glycol derivative such as dibutylmethylenebisthioglycolate, glycerol monoacetate, glycerol triacetate, glycerol derivative such as glycerol tributyrate, epoxy Soybean oil, Epoxy butyl stearate, Epoxy hexahydrophthalate di-2-ethylhexyl, Epoxy hexahydrophthalate diisodecyl, Epoxy triglyceride, Epoxidized octyl oleate, Epoxidized decyl oleate and other epoxy derivatives, Adipic acid polyester Polyester plasticizers such as sebacic acid polyester and phthalic acid polyester, or partially hydrogenated terphenyl, adhesive plasticizer, further diallyl phthalate, Although such polymeric plasticizers such as Lil-based monomer or oligomer can be cited, it is preferred that the phthalate in these. One of these plasticizers
They may be used alone or in combination of two or more.

The component (C) filler 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. , Fine particles of inorganic substances such as silicic acid anhydride and calcium carbonate, organic / inorganic composite thixotropic agents, organic thixotropic agents, etc., and thixotropic agents include silicic acid anhydride such as silicic acid anhydride and hydrous silicic acid and bentonite such as organic bentonite and silo. Asbestos such as dex and organic such as dibenzylidene sorbitol can be used, and any of those added to the composition of polyvinyl chloride resin and plasticizer can be used.

A filler having an average single particle diameter 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.

In the plastigel of the present invention, the viscosity can be changed by the particle size and content of the particles dispersed in the plastigel and the amount of the plasticizer. The present invention provides an acrylic acid having an average single particle diameter of 5 μm or less, which is used under conditions such as the amount of resin and the ratio of plasticizer, the type of plasticizer, and other additives, which are determined according to the required properties of the molded product. It is characterized in that the viscosity of the plastigel is adjusted to a specific high viscosity by appropriately selecting the particle size and amount of the ester copolymer and the particle size and amount of the filler having a particle size of 0.5 μm or less.

The plastigel of the present invention has an average single particle size of 0.5 μm or less with respect to 100 parts by weight of the acrylic ester copolymer in the plastigel in order to achieve a high viscosity under the above-mentioned conditions. It is possible to mix 20 to 150 parts by weight of the filler and 40 to 80 parts by weight of the plasticizer in a ratio range. In this case, if the compounding 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 150 parts by weight, the thixotropy is lowered and the shape of the shaped gel is fixed by heating. It is easy to collapse in front. Further, when the compounding ratio of the plasticizer is more than 80 parts by weight, the viscosity of the plastigel is too low, and when 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. Examples of preferable dissolved polymers include polyvinyl chloride, NBR, EVA, and acrylic acid ester-based copolymers themselves. As long as it is soluble in other plasticizers and can increase the viscosity, it can be used without particular limitation. Further, as another method of increasing the viscosity, a method of heat-treating a dispersion of an acrylic acid ester-based copolymer and a plasticizer to appropriately absorb and swell the plasticizer into the acrylic acid ester-based copolymer is also used. it can. If the dispersion of the acrylic acid ester-based copolymer and the plasticizer is excessively heated, it will gel, so it is necessary to appropriately heat the dispersion. In addition, compounding agents that are usually used for processing polyvinyl chloride, such as diluents, stabilizers, pigments, and ultraviolet absorbers, can be optionally used.

In addition, optional additives such as diluents, stabilizers, ultraviolet absorbers, pigments such as titanium dioxide, litharge, lithopone, zinc oxide and carbon, which are usually used for processing polyvinyl chloride, are optionally used. Yes, this also changes the viscosity of the plastigel. The plastigel composition of the present invention has an average single diameter of 5 μm or less so as to be a high-viscosity product in the above viscosity range, depending on various formulations, if desired, added to plastigel to affect the viscosity, and depending on the resin content. By selecting the blending amount of the resin particles and the blending amount of the filler of 0.5 μm or less, it is possible to obtain a specific high viscosity of the plastigel of the present invention. In the present invention, the viscosity of plastigel at room temperature has a shear rate of 1 sec ^-1 to 500,000 cps to 5,000,000 cps and a shear rate of 1
The viscosity must be 500,000 cps or less at 00 sec ^-1 .

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 when the plastigel is filled in the mold, it will flow and flow out from the open part. 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. 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 peripheral edge of the glass by using an extruder as shown in FIG. 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 with a spatula etc. to a continuous curved surface. 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 having a 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.

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.

[0028]

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 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 above sheets were 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, 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
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, with the glass surface horizontal, in a hot air oven at 140 ° 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> 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.

[0030]

[Table 1]

Note 1) Resin: 90 wt% methyl methacrylate, 10 wt% butadiene acrylic acid ester copolymer, average particle size 0.1 μm 2) Resin: 85 wt% methyl methacrylate, 10 wt% isoprene, 5 wt% glycidyl methacrylate acrylic acid Ester copolymer, average particle size 0.3 μm 3) Resin: 75 wt% methyl methacrylate, 10 wt% ethyl acrylate, 10 wt% butadiene, 5 styrene
wt% acrylic acid ester copolymer, average particle size 0.3μ
m 4) Zeon resin 43F: vinyl chloride resin manufactured by Nippon Zeon Co., Ltd. 5) Epoxy resin: bisphenol A manufactured by Asahi Denka Kogyo 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 Example 2,
A gasket having strong adhesion to the glass and not easily peeled was obtained. In Comparative Example 3, the plastigel was smoothly discharged from the discharge mouthpiece, but the desired shape could not be maintained and it immediately flowed out. In Comparative Example 4, the plastigel is not completely dissolved.

[0033]

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 is also an advantage. 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.

[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.

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.

[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

Claims (3)

[Claims] 1. A main constituent unit (A) is (a) an alkyl group having an alkyl group having 1 to 8 carbon atoms, and /
Alternatively, 100 parts by weight of an acrylic acid ester-based copolymer having an average single particle size of 5 μm or less, which is composed of 98 to 50% by weight of a methacrylic acid alkyl ester unit and 2 to 50% by weight of a (b) diene-based monomer unit, and , (B) 40 to 80 parts by weight of a plasticizer and (C) a filler 2 having an average single particle size of 0.5 μm or less.
It is a plastigel dispersed in 0 to 150 parts by weight and has a viscosity at room temperature of 50 at a shear rate of 1 sec ^-1 .
A plastigel composition having a viscosity of 10,000 cps or more and 5 million cps or less and a viscosity of 500,000 cps or less 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 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.