JPH05271511A - Plastigel composition and molded article using the same - Google Patents

Abstract

PURPOSE:To obtain a plastigel composition capable of readily and accurately producing molded articles free from burr at normal temperature under normal pressure by using a simple device by dispersing a plasticizer and a specific filler into resin fine particles having a specific double layer structure. CONSTITUTION:(B) 40-80 pts.wt. plasticizer (preferably pyromellitic ester-based plasticizer) and (C) 20-150 pts.wt. filler having <=0.5mum average uniform particle diameter are dispersed into (A) 100 pts.wt. A1: fine particles consisting of a shell part composed of a continuous layer of a methyl methacrylate-based or acrylonitrile-based resin having >=50 deg.C second-order transition point and a nucleus part composed of a diene-based rubberlike polymer or A2: fine particles consisting of a shell part composed of a continuous layer of a vinyl chloride- based polymer and a nucleus part composed of an acrylate-based, diene-based and/or styrenic rubberlike polymer to give the objective plastigel composition having 50,000-5,000,000 CPS viscosity at 1/sec shear rate and 500,000 CPS at 100/sec shear rate at normal temperature.

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 composition.

[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 greatly to attach it to a part with a large bend, the gasket will wrinkle and the appearance will deteriorate, In addition, there is a problem that it is difficult to install. 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 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 problem, 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. Further, for example, when the cross-sectional shape of the gasket has a thin wall portion of about 0.5 to 2 mm, there is a defect that this portion is extremely 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. Focusing on the phenomenon of abrupt increase, the high viscosity of plastigel is controlled by selecting the blending amount of fine particles and the particle size, and the outer shell of the particles is made into a resin layer and the core is made of rubber-like polymer. Therefore, the inventors have found that the problems of burr generation and bubbles can be solved, and have completed the present invention based on this finding.

That is, the present invention comprises (a) an outer shell portion composed of a continuous layer of a methyl methacrylate or acrylonitrile resin having a second-order transition point of 50 ° C. or higher, and a core portion composed of a diene rubber-like polymer. Fine particles, or
(B) 40 parts by weight of a plasticizer to 100 parts by weight of fine particles composed of an outer shell part composed of a continuous layer of a vinyl chloride polymer and a core part composed of an acrylate, diene and / or styrene rubbery polymer. A plastigel in which 80 parts by weight and 20 to 150 parts by weight of a filler having an average single particle size of 0.5 μm or less are dispersed, wherein the viscosity at room temperature is 500,000 cps or more and 5,000,000 cps or less 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 article produced using the composition.

The plastigel of the present invention is a plastigel having a high viscosity such that it does not deform due to 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
It has been shown to have a viscosity of less than 0,000 cps and less than 500,000 cps at a shear rate of 100 ^-1 . The resin fine particles used in the present invention include the two types of the above (a) and (b). In the first fine particles (a), the outer shell has a second-order transition point (T
g) is a fine particle having a two-layer structure comprising a continuous layer of an acrylate-based or acrylonitrile-based resin having a temperature of 50 ° C. or higher, and the core of the core of which is a diene-based rubber-like polymer.

When the resin constituting the outer shell of the polymer fine particles (a) has a Tg of less than 50 ° C., the non-aqueous liquid dispersion medium permeates the inside of the particles at room temperature and the paint thickens with time and is sprayed. It may not be possible to paint. A methylmethacrylate resin or an acrylonitrile resin is used as the resin forming the outer shell. The former methyl methacrylate resin has a Tg of 50.
There is no particular limitation as long as it is at least ℃, and for example, methyl methacrylate homopolymer or methyl methacrylate as a main component is contained in an amount of 50% by weight or more, preferably 60% by weight or more, particularly preferably 70% by weight or more. A copolymer with another monomer copolymerizable therewith is preferably used. As the copolymerizable monomer, ethyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate and the like can be used.

As the acrylonitrile resin,
For example, an acrylonitrile-styrene copolymer having a Tg of 50 ° C or higher, an acrylonitrile-vinylidene chloride copolymer, an acrylonitrile-methyl methacrylate copolymer, an acrylonitrile-N-phenylmaleimide copolymer, an acrylonitrile-styrene-acrylic rubber copolymer, Acrylonitrile-EPDM-styrene copolymer,
Acrylonitrile-butadiene-styrene copolymer and the like can be used. Among these resins for the outer shell layer, a methyl methacrylate homopolymer is particularly suitable. In the present invention, the secondary transition point of the resin of the outer shell layer is
The same resin as the outer shell layer resin was manufactured separately under the same polymerization conditions used when forming the outer shell portion, and the second-order transition point of this resin was measured using a rheometrics dynamic spectrometer (Rheometrics). What is measured by is regarded as the second-order transition point of the resin for the outer shell layer.

On the other hand, examples of the diene rubber-like polymer forming the core include polybutadiene, styrene-butadiene copolymer, polyisoprene, butadiene-isoprene copolymer, natural rubber and the like. Polybutadiene and styrene-butadiene copolymer are preferable, and styrene-butadiene copolymer is particularly preferable. This styrene-butadiene copolymer has a random type and a block type, and both can be preferably used. The second resin fine particles (b) are two-layer structure fine particles composed of a vinyl chloride polymer whose outer shell forms a continuous layer and whose core comprises an acrylate-based, diene-based or styrene-based rubber-like polymer. is there. In this polymer particle, the vinyl chloride polymer forming the outer shell is
It may be a vinyl chloride homopolymer, or contains vinyl chloride as a main component in an amount of 50% by weight or more, preferably 60% by weight or more, particularly preferably 70% by weight or more. It may be a copolymer. Examples of the copolymerizable monomer include fatty acid vinyl ester,
Vinylidene halide, acrylic acid alkyl ester, methacrylic acid alkyl ester, acrylonitrile, alkyl vinyl ether, allyl alcohol, styrene and derivatives thereof can be used.

Since these resins have a second-order transition point of 50 ° C. or higher as viewed from the structural unit of the resin, it is not necessary to add the requirement for the fine particles (a). On the other hand, the acrylate-based rubber-like polymer constituting the core portion, for example the alkyl esters of C ₄ -C ₁₆ of such acrylic acid butyl acrylate as a main component 50% by weight or more, preferably 60 wt% or more, particularly preferably Is 70% by weight or more, and a monomer copolymerizable therewith, such as methyl methacrylate, ethyl acrylate, 2-chloroethyl vinyl ether, glycidyl (meth) acrylate, allyl glycidyl ether, ethylidene norbornene, triallyl trimellitate, etc. And the like. As the diene rubbery polymer, the same ones as those used for the polymer fine particles (a) can be used.

Further, examples of the styrene rubber-like polymer include a styrene block copolymer having a polystyrene block and a rubber intermediate block. Specifically, the rubber intermediate block is S-B-S of polybutadiene and S of polyisoprene. -IS, S-EB-S of polyolefin (ethylene / butylene), polyolefin (isobutylene)
S-IB-S and the like. Among the above rubber-like polymers, polybutadiene and S-B-S can be used particularly preferably.

The resin fine particles having such a two-layer structure can be manufactured, for example, as follows. First, a latex containing rubber-like polymer particles that form the core of resin fine particles is prepared by ordinary emulsion polymerization or fine suspension polymerization,
Then, using the anionic or nonionic surfactant with the rubber-like polymer particles in the latex or the particles obtained by aggregating and enlarging the rubber-like polymer particles as a nucleus, a monomer that forms the outer shell of the polymer particles in an aqueous medium is used. By performing emulsion polymerization of and further enlarging the particles,
An outer shell layer is formed to obtain desired polymer fine particles. The diameter of the core particles composed of the rubber-like polymer used at this time is usually in the range of 0.1 to 49 μm, and the outer shell layer is formed on this.

In the emulsion polymerization of the above-mentioned outer shell forming monomer, a water-soluble polymerization initiator or a redox initiator is used as a catalyst. Examples of the water-soluble polymerization initiator include potassium persulfate, ammonium persulfate, azobisisobutylamidine hydrochloride, azobiscyanovaleric acid and the like. On the other hand, as the redox type initiator, a combination of a water-soluble reducing agent and an organic peroxide is usually used. Examples of the water-soluble reducing agent in the redox type initiator include ethylenediaminetetraacetic acid or its sodium salt or potassium salt, or a complex compound of these with a heavy metal such as iron, copper or chromium, sulfinic acid or its sodium salt or potassium salt. , 1-ascorbic acid or its sodium salt, potassium salt, calcium salt, ferrous pyrophosphate, ferrous sulfate, ferrous ammonium sulfate, sodium sulfite, sodium acid sulfite, sodium formaldehyde sulfoxylate, reducing sugars, etc. Named
These can be used alone or in combination of two or more.

Examples of the organic peroxide in the redox type initiator include cumene hydroperoxide and p
-Cymen hydroperoxide, t-butyl isopropyl benzene hydroperoxide, diisopropyl benzene hydroperoxide, p-menthane hydroperoxide, decalin hydroperoxide, t-amyl hydroperoxide, t-butyl hydroperoxide, isopropyl hydroperoxide and other hydroperoxides. Be done. These organic peroxides may be used alone or in combination of two or more.

Further, as the anionic surfactant used in the emulsion polymerization, 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 ester sulfate ester salt, polyoxyetherene alkylphenyl ether sulfate ester salt, polyoxyethylene alkylphenyl ether acidity Examples include phosphoric acid esters and salts thereof, succinic acid dialkyl ester sulfonates, etc.
One kind may be used, or two or more kinds may be used in combination.

Examples of nonionic surfactants include polyoxyethylene alkylphenyl ethers,
Intramolecular polyoxyethylene chains such as polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether glycerin borate ester, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene, etc. And a compound having surface activity and a polyoxyethylene chain of the compound being replaced by a copolymer of oxyethylene and oxypropylene, further sorbitan fatty acid ester, fatty acid glycerin ester, glycerin fatty acid ester, penta Examples thereof include erythritol fatty acid ester, and these may be used alone or in combination of two or more.

The amount of the above-mentioned water-soluble polymerization initiator, redox type initiator, organic peroxide, anionic surfactant and nonionic surfactant used should be appropriately selected from those used in ordinary emulsion polymerization. You can In this way, a latex in which fine polymer particles having a core / shell two-layer structure are uniformly dispersed can be produced. This latex is usually subjected to a known treatment such as salting out or spray drying,
The polymer fine particles are taken out as a solid. In the present invention, the above-mentioned two kinds of polymer fine particles may be used alone or in combination of two or more kinds, and if necessary, within a range not impairing the object of the present invention, a core / shell bilayer. It can be used in combination with non-structured single-layer structure polymer particles.

The plasticizer used in the present invention has an affinity for the rubber-like polymer in the core of the polymer particles and has a distillate content of 10% by weight or less when heated to 200 ° C. at room temperature. Those are preferable. Examples of such compounds include di- (2-ethylhexyl) phthalate, di-n-octylphthalate, diisobutylphthalate, diheptylphthalate, diphenylphthalate, diisodecylphthalate, ditridecylphthalate, diundecylphthalate, di (heptyl, nonyl. ,
Undecyl) phthalate, benzyl phthalate, butyl benzyl phthalate, dinonyl phthalate, dicyclohexyl phthalate, and other phthalic acid derivatives, corresponding isophthalic acid derivatives and tetrahydrophthalic acid derivatives, di-n-butyl adipate, di- (2-ethylhexyl) Adipic acid derivatives such as adipate, diisodecyl adipate, diisononyl adipate, azelaic acid derivatives such as di- (2-ethylhexyl) azelate, diisooctyl azelate, di-n-hexyl azelate, di-n-butyl sebacate, di- ( 2-ethylhexyl) sebacate and other sebacic acid derivatives, tri-
Trimellitic acid such as (2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisodecyl trimellitate, triisooctyl trimellitate, tri-n-hexyl trimellitate, triisononyl trimellitate Derivatives, pyromellitic acid derivatives such as tetra- (2-ethylhexyl) pyromellitate, tetra-n-octylpyromellitate, triethyl citrate, tri-n-butyl citrate, acetyltriethyl citrate, acetyltri- (2-ethylhexyl) )
Citric acid derivatives such as citrate, monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, itaconic acid derivatives such as di- (2-ethylhexyl) itaconate, butyl oleate, glyceryl monooleate,
Oleic acid derivatives such as diethylene glycol monooleate, methylacetyl ricinoleate, butylacetyl ricinoleate, glyceryl monoricinoleate, ricinoleic acid derivatives such as diethylene glycol monoricinoleate, n-butyl stearate, glycerin monostearate, diethylene glycol distearate, etc. Other fatty acid derivatives such as stearic acid derivative, diethylene glycol monolaurate, diethylene glycol dipelargonate, pentaerythritol fatty acid ester, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di- (2- Ethyl butyrate), triethylene glycol di- (2-
Ethyl hexoate), dibutyl methylene bisthioglycolate, glycol derivatives such as 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, glycerol triacetate, glycerin derivatives such as glycerol tributyrate, 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, and further hydrochloric paraffin, Epoxidized soybean oil, tar fractions, glycol ethers, waste lubricating oils, naphthenic or aromatic process oils, cyclic naphthenic hydrocarbons, terpenes, etc. .

Among these plasticizers, those which give a coating film excellent in film physical properties such as tensile strength and elongation and non-bleeding property are those having a molecular weight of 500 or more and a dielectric constant at 25 ° C. of 5 or less. Ester type ester,
It is a naphthenic process oil containing 10% or more of aromatics and 35% or more of naphthenes. These non-aqueous liquid dispersion media may be used alone or in combination of two or more. 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. Examples include fine particles of inorganic substances, organic / inorganic composite thixotropic agents, organic thixotropic agents, and the like.Thixotropic agents include silicic acid anhydride, silicic acid such as hydrous silicic acid, bentonite such as organic bentonite, and asbestos such as silodex and dibenzylidene. Organic materials such as sorbitol can be used, and any material added to the composition of the polyvinyl chloride resin and the 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.

The 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 and improving the dimensional accuracy of the molded product. 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 relates to the particle size and blending ratio of the two-layer structure resin fine particles used under the determined conditions such as the amount of resin and the ratio of the plasticizer, the type of the plasticizer, and other additives, which are determined according to the required properties of the molded product. The feature is that the viscosity of the plastigel is adjusted to a specific high viscosity by appropriately selecting the amount and the particle size and blending amount of the filler of 0.5 μm or less.

The plastigel of the present invention has an average single particle size of 0.5 μ with respect to 100 parts by weight of the resin (A) in the plastigel in order to achieve a high viscosity under the above-mentioned conditions.
20 to 150 parts by weight of a filler of m or less and 40 to 8 of a plasticizer
It can be blended in the range of the ratio of 0 parts by weight. 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. Preferred soluble 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. 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, titanium dioxide, litharge, lithopone, zinc oxide, pigments such as carbon, etc., which can be usually used for polyvinyl chloride processing, can be optionally used, which also changes the viscosity of plastigel. ..

The plastigel composition of the present invention contains various compounds which are optionally added to plastigel, and the amount of resin fine particles and the amount of the resin fine particles are adjusted so as to obtain a highly viscous product in the above viscosity range with respect to the viscosity change depending on the resin content. By appropriately selecting the compounding amount of the filler of 0.5 μm or less, the plastigel of the present invention can be adjusted to a specific high viscosity without fail. In the present invention, the viscosity at room temperature Purasuchigeru at a shear rate of 1 sec ^-1 500,000 cps or 5 million cps or less, it is necessary that the viscosity of below 500,000 cps at a shear rate 100 sec ^-1. The viscosity of plastigel is 500,000c at a shear rate of 1 sec ^-1.
If it is smaller than ps, there is a risk that when 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. Shear rate 100
If sec ⁻¹ is more than 500,000 cps, 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 but also improves the dischargeability. It is inferior and cannot be molded 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 portion 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 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 gives a sufficient amount of heat for melting, but can be easily heated by any method used for melting plastisol, such as hot air, high frequency dielectric heating, and high frequency induction heating. ..

By using the plastigel of the present invention,
It is possible to accurately manufacture a molded product having a complicated shape and a molded product having a thin wall portion by a simple operation. Furthermore, it is desirable that the plastigel used in the present invention has adhesiveness to glass or the like that is formed by contact with it. In order to impart adhesiveness to glass or the like to the plastigel of the present invention, a method of converting methyl methacrylate or vinyl chloride-based polymer forming the outer shell of the resin (A) into a copolymer with another functional group-containing monomer is used. 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. 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, 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 is
It can be evaluated by a 90 ° peel test. In the present invention, this adhesive strength is 1 kg / cm (tensile strength 200 mm /
min) or more, especially 3 kg / cm or more.

[0028]

EXAMPLES The present invention will be described in more detail with reference to the following examples. Production Example 1 Production of Resin Powder (1) A latex containing styrene-butadiene copolymer rubber (SBR) particles having a styrene unit content of 26 wt% was prepared by emulsion polymerization, and then methyl methacrylate was emulsified with the SBR particles as cores. Polymerization was carried out to prepare a resin powder (1) of polymer particles having an average particle size of 0.50 μm, in which the core portion was made of SBR and the outer shell portion was made of a continuous polymethylmethacrylate layer having an average thickness of 0.07 μm. The Tg of the methacrylate resin polymerized under the same conditions as the emulsion polymerization was 11
It was 0 ° C.

Production Example 2 Production of Resin Powder (2) A latex containing poly n-butyl acrylate particles obtained by copolymerizing 5 wt% of glycidyl methacrylate and 1 wt% of triallyl trimellitate was prepared by emulsion polymerization. -Emulsion polymerization of vinyl chloride using butyl acrylate particles as a core, the core of which is made of poly-n-butyl acrylate, and the outer shell of which is a continuous polyvinyl chloride layer having an average thickness of 0.1 .mu.m. A resin powder (2) having polymer particles of 62 μm was produced. The Tg of the vinyl chloride resin polymerized under the same emulsion polymerization conditions as described above was 87 ° C.

Production Example 3 Production of Resin Powder (3) A latex containing methyl methacrylate-butyl acrylate copolymer particles containing 40 wt% of butyl acrylate units was prepared by emulsion polymerization, and the copolymer particles were used as a core. 30 wt% of acrylonitrile and 70 wt% of styrene were emulsion-polymerized to prepare a resin powder (3) of polymer particles having an average particle size of 0.45 μm. The Tg of the acrylonitrile-styrene copolymer resin polymerized under the same emulsion polymerization conditions as above was 120 ° C.

Production Example 4 Production of Resin Powder (4) A latex containing polybutadiene particles having an average particle size of 0.1 to 0.3 μm was prepared by emulsion polymerization, and then butadiene was stirred under strong stirring at a temperature of Tg or higher. The average particle size is 0.8μBR by adding a monomer and coagulating the solvent.
An aggregated particle dispersion was obtained. Next, 90% by weight of methyl methacrylate and 10% by weight of glycidyl methacrylate were graft-polymerized to this dispersion of agglomerated particles, whereby the core portion was made of the BR aggregate and the outer shell portion had an average thickness of 0.05 μm.
A resin powder (4) having polymer particles having an average particle size of 0.90 μm, which is composed of a continuous methylmethacrylate-glycidylmethacrylate copolymer layer, was prepared. The methyl methacrylate-glycidyl methacrylate copolymer copolymerized under the same emulsion polymerization conditions as described above had a Tg of 103 ° C.

Examples 1 to 4 and Comparative Examples 1 to 4 The respective raw materials shown in Table 1 were mixed with a Hobart type 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 sheet is cut into three 50 mm × 100 mm sheets,
Spring type hardness test (A type) by stacking 3 sheets
The hardness was measured with. (Refer to JIS K6301) Shape after heating FIG. 1 shows a device for directly ejecting plastigel to the glass peripheral edge portion of the present invention, and a plastigel attached to the glass peripheral edge portion while ejecting the plastigel from a gun mouthpiece having a predetermined shape. It is a perspective view showing the state where it is made. 1 is glass, 2 is ejected plastigel, 3 is gun ejection cap,
4 indicates a plastigel supply hose. Put the above-mentioned plastigel in the tank and pressurize it with a snake pump to 10 mm.
From hose 4 with φ inner diameter 50 from gun outlet 3
Discharge at cc / min, and move to the periphery of glass with a thickness of 30 cm × 50 cm × 3 mm, and the maximum thickness in the direction perpendicular to the glass surface 2
A gel having a width of 0 mm and a width of 10 mm in the horizontal direction was attached, and the glass surface was kept horizontal and heated in a hot air oven at 140 ° C. for 15 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 ROTOVIS
CO RV-3 sensor: Cone plate type PK-1-3 ° Hydrogen chloride gas generation amount Peel off a part of the coating film of 3 mm thickness according to the case of the electric wire.
The amount of hydrogen chloride gas generated when incinerated is measured according to JIS K7228,
It was measured according to JIS K0107. Table 1 shows the evaluation results of Examples and Comparative Examples.

[0035]

[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 Kogyo 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 all of Examples 1, 2, 3, and 4, the ejection of plastigel from the ejection nozzle was smooth, the cross-sectional shape maintained a predetermined shape, and the shape changed 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 the plastigel immediately flowed out. Comparative Example 1 caused a deformation in which the maximum thickness was reduced. Comparative Example 2 could not be discharged. In Comparative Example 4, a large amount of hydrochloric acid was generated, and the physical properties collapsed and the shape could not be maintained.

[0038]

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

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[Procedure amendment]

[Submission date] May 14, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0030

[Correction method] Change

[Correction content]

Production Example 3 Production of Resin Powder (3) A latex containing methyl methacrylate-butyl acrylate copolymer particles containing 40 wt% of butyl acrylate units was prepared by emulsion polymerization, and the copolymer particles were used as a core. Emulsion polymerization of 50 wt% acrylonitrile and 50 wt% styrene gives an average particle size of 0.45
A resin powder (3) of polymer particles of μm was produced. The Tg of the acrylonitrile-styrene copolymer resin polymerized under the same emulsion polymerization conditions as above was 120 ° C.

Claims (3)

[Claims] 1. (a) Fine particles composed of an outer shell portion composed of a continuous layer of a methyl methacrylate-based or acrylonitrile-based resin having a second-order transition point of 50 ° C. or higher, and a core portion composed of a diene rubber-like polymer, or And (b) 100 parts by weight of fine particles composed of an outer shell part composed of a continuous layer of a vinyl chloride polymer and a core part composed of an acrylate-based, diene-based and / or styrene-based rubbery polymer, with respect to 40 parts by weight of a plasticizer. ~
A plastigel in which 80 parts by weight and 20 to 150 parts by weight of a filler having an average single particle size of 0.5 μm or less are dispersed, having 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 solid chloride obtained by heating the plastigel at a temperature of 150 ° C. for 30 minutes has a hydrogen chloride gas generation amount of 50 mg / g or less upon combustion. 3. A molded product obtained by extruding the composition of claim 1 or 2 from a die under normal temperature and normal pressure to obtain a molded product, which is obtained by heating and melting the molded product.