KR100868433B1 - Poly vinyl chloride composition for glass encapsulation injection molding of vehicle - Google Patents

Abstract

A PVC composition for glass encapsulation injection molding of vehicle is provided to prevent the failure of non-molding and to ensure a melt flow index. A PVC composition for glass encapsulation injection molding of vehicle comprises 100 parts by weight of polyvinyl chloride having a DP(Degree of Polymerization, JIS K6721-77) of 400-700 (or, 52-60 of the K-value 52, DIN 53726); 30-60 parts by weight of plasticizer containing at least one of dioctylphthalate(DOP), diisodecyl phthalate(DIDP), diisononylphthalate(DINP), diethylhexyl phthalate(DEHP), di-n-octyl phthalate(DNOP), dibutyl phthalate(DBP), butyl benzyl phthalate(BBP) at least and the non-phthalate plasticizer made of one among the alkyl sulfonic acid (mesamoll) of the cresol and di -2- hexyl adipate(DOA), tree ethylhexyltrimelliatate(TOTM), acetyl tributyl citrate(ATBC), phenol, the diisononyladipate(DINA), and the mono glycerine; 20-50 parts by weight consisting of at least one of calcium carbonate, talcum, and muscovitum; 3-8 parts by weight of thermal stabilizer consisting of at least one of epoxy-based thermal stabilizer, Ba-Zn-based thermal stabilizer, Ca-Zn-based thermal stabilizer, hydrotalcite-based thermal stabilizer and zeolite-based thermal stabilizer; 1-10 parts by weight of impact modifier containinig a methylmethacrylate-butadiene-styrene copolymer; 0.1-2 parts by weight of processing aid; 0.1-2 parts by weight of lubricant; 0.1-3 parts by weight of UV stabilizer; and 0.1-1 parts by weight of antioxidant. In the shore-A hardness is 80-95, 175 deg.C, and 5.0kg load, the melt index (M/I) is 50-100g/min.

Description

POLY VINYL CHLORIDE COMPOSITION FOR GLASS ENCAPSULATION INJECTION MOLDING OF VEHICLE}

The present invention relates to a polyvinyl chloride composition for vehicle encapsulation glass molding, and more particularly, in a polyvinyl chloride (PVC) composition for sealing between a door glass and a door of an automobile, a melt flow index is It is high and relates to a polyvinyl chloride composition which is applied to prevent unformed defective rate.

In general, the door of the vehicle (vehicle) is not only hinged to the frame so that the occupant can get on and off, the door glass is mounted so that the door glass can be lifted and lifted without opening the door. That is, the door glass is installed in the door to be lifted by the regulator assembly, when the door glass is lifted, the sealing structure is installed to shield the inside and outside of the vehicle, the insulation structure is insulated It is called encapsulation.

A method for producing an encapsulation of the vehicle is described, for example, in Korean Laid-Open Patent Publication No. 2002-0054783, "Injection Mold for Glass Encapsulation of a Vehicle." In order to manufacture the insulation glass of such a vehicle, the glass is inserted into a mold, the mold core is closed, and a mold (injection product) made of a polyvinyl chloride (PVC) composition is injected to manufacture a glass and a mold assembly. In this process, if the melt flow index of the polyvinyl chloride (PVC) composition is low, the defect rate is high due to the unmolding of the product. In addition, when the injection pressure is increased to improve the defective rate of unmolding, pressure is transmitted to the inserted glass, thereby increasing the breakage rate and lowering the process yield, thereby causing the cost increase.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a polyvinyl chloride composition that satisfies the physical properties that can be used for molding in insulation glass of a vehicle while having a high melt index.

The present invention is to solve the above problems, the polyvinyl chloride composition for vehicle encapsulation glass molding capable of low-pressure injection according to the present invention, the degree of polymerization 400 (PDP) (Degree of Polymerization, JIS K6721-77) 400 to 700 (or Polyvinyl chloride (PVC) having a K value of 52 to 60 (DIN 53726) and 100 parts by weight of the polyvinyl chloride; Dioctylphthalate (DOP), Diisodecylphthalate (DIDP), Diisononylphthalate (DINP), Diethylhexylphthalate (DEHP), Di-n-octylphthalate (DNOP), Dibutylphthalate (DBP), Butylbenzyl Phthalate plasticizer consisting of at least one of phthalates (BBP) and di-2-hexyl adipate (DOA), tri-ethylhexyl trimellitate (TOTM), acetyltributyl citrate (ATBC), alkyl sulfonic acids of phenol and cresol 30 to 60 parts by weight of a plasticizer composed of at least one of a nonphthalate plasticizer composed of at least one of (mesamol), diisononyl adipate (DINA), and monoglycerine; 20 to 50 parts by weight of a filler; 3 to 8 parts by weight of a heat stabilizer; 1 to 10 parts by weight of an impact modifier; 0.1 to 2 parts by weight of processing aids; 0.1 to 2 parts by weight of lubricant; 0.1-3 parts by weight of UV stabilizers; It comprises 0.1 to 1 parts by weight of antioxidant, the Shore-A hardness is 80 to 95, 175 ℃, the melt index (M / I) is 50 to 100g / min load.

Here, the filler is preferably at least one of calcium carbonate, talc, mica in order to exert the minimum and maximum effects of the extrusion amount, rigidity, heat deformation temperature improvement.

In addition, the thermal stabilizer is hydrogen chloride generated from the dehydrochlorination reaction generated during PVC processing of at least one of a Sn-based heat stabilizer, Ba-Zn-based Ca-Zn-based, hydrotalcite-based, zeolite-based, epoxy-based thermal stabilizer ( It is preferred to play a role of rapidly neutralizing HCl).

In addition, the impact modifier is at least one of methyl methacrylate- butyl acrylate copolymer, acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, and the like It is desirable to increase the warpage and impact strength.

Meanwhile, the processing aid is methyl methacrylate, and the antioxidant is divinyl benzene, triallyl cyanurate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, polyethylene glycol diketacrylate, trimethylol It is preferable that it is at least one of propane triketacrylate and allyl methacrylate.

In addition, the ultraviolet stabilizer is preferably at least one of a hydroxybenzophenone-based, benzotriazole-based, substituted acrylate-based, hindered amine (Hindered Amine) -based ultraviolet stabilizer.

According to the present invention, since the injection is possible at a low pressure with a high melt index, it is possible to reduce the defective rate due to unmolding when manufacturing the insulation glass of the vehicle, and improve the production yield by reducing the glass breakage rate.

Hereinafter, the present invention will be described in detail.

The polyvinyl chloride composition for vehicle encapsulation glass molding according to the present invention has a polyvinyl chloride (PVC) having a degree of polymerization 400 to 700 (or K value 52 to 60 (DIN 53726)) of DP (Degree of Polymerization, JIS K6721-77). PVC) 100 parts by weight, plasticizer 30 to 60 parts by weight, filler 20 to 50 parts by weight, heat stabilizer 3 to 8 parts by weight, impact modifier 1 to 10 parts by weight, processing aid 0.1 to 2 parts by weight, lubricant 0.1 to 0.1 It comprises 2 parts by weight, UV stabilizer 0.1 to 3 parts by weight, antioxidant 0.1 to 1 part by weight.

The degree of polymerization of the polyvinyl chloride (PVC) resin in the composition is preferably a relatively low polymerization resin of DP 400 to 700 (K value 52 to 60) in order to improve flow characteristics such as melt index, and the degree of polymerization The use of PVC resin outside the range improves mechanical properties, but the above-described problems may occur due to a sharp drop in the melt index. However, since the low-polymerization PVC resin is used, disadvantages may occur in that physical properties such as gas generation, heat stability, light resistance, etc. may be weakened. To compensate for this, a resin stabilizer, a filler, and the like are added.

Since PVC resin is a hard and brittle glassy material at normal temperature, it can make molding process easy by adding a plasticizer to this and lowering melting temperature and melt viscosity. Generally, plasticizers are inert liquids, which play a role similar to that of solvents, but differ from solvents in that they have a high molecular weight and are difficult to volatilize compared to solvents.

As the plasticizer used in the present invention, a phthalate plasticizer and a nonphthalate plasticizer are used alone or in combination, and the phthalate plasticizer is dioctylphthalate (DOP), diisodecyl phthalate (DIDP), and diisononyl phthalate (DINP). ), Diethylhexyl phthalate (DEHP), di-n-octyl phthalate (DNOP), dibutyl phthalate (DBP), butyl benzyl phthalate (BBP), or the like. Di-2-hexyl adipate (DOA), tri-ethylhexyl trimellitate (TOTM), acetyltributyl citrate (ATBC), alkyl sulfonic acid (mesamol) of phenol and cresol, diisononyl adipate ( DINA), monoglycerine, and the like are preferably used alone or in combination. In addition, as a secondary plasticizer, chlorinated paraffin, epoxidized soybean oil, fatty acid plasticizer, etc. can also be added and used suitably.

The plasticizer is preferably added in an amount of 30 to 60 parts by weight, more preferably 40 to 50 parts by weight based on 100 parts by weight of the PVC resin of the PVC composition according to the present invention. It is difficult to secure the above-described melt index and processability, if the content exceeds 60 parts by weight, there is a problem that it is difficult to obtain a constant strength for applying for the vehicle insulation glass of the finished injection.

The fillers used in the present invention are calcium carbonate (CaCO ₃ ), talc (talc, Mg ₃ (OH) ₂ Si ₄ O ₁₀ ), mica, and more preferably calcium carbonate. The filler used in the present invention has a specific gravity of 2.9 to 3.2, and has a relatively high specific gravity compared to other components of the PVC composition. Therefore, when the filler such as calcium carbonate is added to the PVC composition of the present invention, the specific gravity of the raw material is increased to increase the extrusion amount.

The addition of the filler is intended to improve the rigidity and heat distortion temperature. In addition, since calcium carbonate is inexpensive, production costs can be reduced. The blending amount of the filler capable of exhibiting the minimum and maximum effects of the extrusion amount, the rigidity and the heat deformation temperature improvement is added to 20 to 50 parts by weight, more preferably 30 to 40 parts by weight based on 100 parts by weight of the PVC resin.

The resin stabilizer used in the present invention includes a heat stabilizer, an impact modifier, a processing aid, a lubricant, an ultraviolet stabilizer (light stabilizer), an antioxidant, and the like, and an antioxidant, an ozone stabilizer, and the like may be applied thereto. In this invention, the said various types of resin stabilizers are used individually or in mixture.

The thermal stabilizer dehydrochlorination occurs during PVC processing, where the thermal stabilizer quickly neutralizes the generated hydrogen chloride (HCl). As a heat stabilizer, non-toxic heat stabilizers such as Sn-based, Ba-Zn-based and Ca-Zn-based metal stabilizers, and non-metal thermal stabilizers such as hydrotalcite-based, zeolite-based and epoxy-based heat stabilizers are used alone or in combination. All. The heat stabilizer is preferably used by adding 3 to 8 parts by weight, more preferably 3 to 5 parts by weight based on 100 parts by weight of the PVC resin. When the heat stabilizer is added in less than 3 parts by weight, the characteristics as the heat stabilizer are not exhibited, and when the heat stabilizer exceeds 8 parts by weight, a large amount of gas is generated.

PVC composition is a polymer containing 50% or more of vinyl chloride (vinyl chloride), and has the disadvantage of being very weak against impact, so that an impact modifier is used to compensate for this disadvantage. In other words, the impact modifier is a fibrous insoluble material added to the plastic to increase the cleavage, tension, compression, warpage, impact strength.

Recently, methyl methacrylate-butadiene-styrene polymerized together with butadiene-based rubber latex and monomers such as styrene and methylmethacrylate or acrylonitrile. (methylmetacrylate-butadiene-styrene: MBS) resin is used.

The physical properties of the methyl methacrylate-butadiene-styrene (MBS) resin are affected by the content of each monomer to be grafted, the polymerization method, and the content and particle size of the rubber latex (latex) used as a substrate. It is known to receive.

The impact modifier used in the present invention is preferably used at least one of acryl-based and MBS (methacrylate-butadiene-styrene) system alone or mixed, more preferably methyl methacrylate-butylacrylate air. Copolymers, acrylonitrile-butadiene-styrene copolymers and methylmethacrylate-butadiene-styrene copolymers are used singly or in combination.

In addition, the impact modifier is preferably added 1 to 10 parts by weight, more preferably 3 to 8 parts by weight based on 100 parts by weight of the PVC resin. When the impact modifier is added less than 1 part by weight, the impact reinforcing effect is insignificant, and when the impact modifier exceeds 10 parts by weight, there is a disadvantage in that it is uneconomical in terms of the effect on the content.

As the processing aid, a medium or low molecular weight methyl methacrylate (MMA) resin is preferably used by adding 0.1 to 2 parts by weight, more preferably 0.3 to 1.5 parts by weight.

Lubricants are added to reduce friction between two surfaces that are in contact with each other and are slippery. They are materials that mix well in the machine and allow the mixed material to melt and slide out of the machine. Although, for example, PE-based wax, stearic acid and its metal salt, that is, dibasic red stearate, dibasic red phosphite, calcium sterate, and the like can be used alone or mixed, the content is 100 parts by weight of the PVC resin With respect to, preferably 0.1 to 2 parts by weight, more preferably 0.3 to 1.5 parts by weight is added.

Ultraviolet rays activate various chemicals, altering their structure and altering their properties, degrading their original properties and functions. Especially, organic pigments used in many resin compounds lose their original properties and functions by being activated by ultraviolet rays. . Therefore, by adding a sunscreen and a UV absorber to the various resin compositions or by performing a surface treatment, the organic material can be protected by absorbing ultraviolet rays of 400 nm or less harmful to organic matter and converting them into harmless thermal energy. Therefore, it does not deteriorate.

UV stabilizers are classified into absorbers, quenchers, and hindered amine light stabilizers (HALS) according to functional mechanisms. According to the chemical structure, it is divided into phenyl salicylates, benzophenone, benzotriazole, benzotriazole, nickel derivative, and radical scavenger, and these are used alone or in combination. do.

Absorber absorbs ultraviolet energy selectively and converts it into infrared energy and emits it. It is used alone or mixed with hydroxy benzophenone, benzotriazole, and substituted acrylic.

The quencher is stabilized by a UV absorber and serves to release energy as fluorescence, phosphorescence, and heat. Mainly nickel compounds are used.

The hindered amine light stabilizer serves to stop the photooxidation reaction by removing the free radicals generated during the photolysis reaction. The hindered amine light stabilizer is easily oxidized and converted into nitroxyl radicals, and reacts with the polymer radicals to produce ethers in hydroxyamines. The photooxidation reaction is then stopped by reacting with peroxide radicals to produce stable nitroxyl radicals.

In addition, examples of the ultraviolet stabilizer include inorganic pigments such as titanium oxide, zinc oxide, iron oxide, hindered phenolic, aromatic phosphite, and the like.

Accordingly, in order to prepare a resin composition stable to ultraviolet rays, a benzotriazole-based sunscreen agent and a hindered phenol having a substituent on a container, resins, films and sheets, packaging resin compositions, etc. Manufacturing by adding UV-based stabilizer can effectively prevent the aging, destruction and deformation of organic compounds by ultraviolet rays, and can extend the shelf life.

In the present invention, the ultraviolet stabilizer is used alone or mixed with a hydroxybenzophenone-based, benzotriazole-based, substituted acrylate-based, hindered amine (Hindered Amine) -based ultraviolet stabilizer, the content is 100 parts by weight of PVC resin Preferably from 0.1 to 3 parts by weight, more preferably from 0.3 to 2.5 parts by weight. When the UV stabilizer is added less than 0.1 parts by weight it is difficult to exhibit the above-described properties of the UV protection, when the content exceeds 3 parts by weight there is a problem that it is uneconomical compared to the content.

The resin stabilizer as an antioxidant is to give the antioxidant effect of the composition during molding processing, divinyl benzene, triallyl cyanurate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, polyethylene glycol diketacrylate , Trimethylolpropane triketacrylate, allyl methacrylate, and phenolic antioxidants may be used alone or in combination, and the content thereof is preferably 0.1 to 1 parts by weight, more preferably 0.2 to 0.8 parts by weight.

Hereinafter, the characteristics of the polyvinyl chloride composition for vehicle encapsulation glass molding according to the present invention through the preferred embodiment of the present invention and evaluation experiments thereof.

Table 1 below is a table showing the composition of preferred compositions of Examples 1 and 2 of the present invention.

TABLE 1

division Example 1 (parts by weight) Example 2 (parts by weight) PVC (polymerization degree DP 700) 100 100 Plasticizer (DIDP: TOTM = 70: 30 wt%) 58 45 Impact modifier (methyl methacrylate-butadiene-styrene copolymer, MBS) 6 7 Filler (Calcium Carbonate) 25 25 Thermal Stabilizer (Ca-Zn Type Thermal Stabilizer) 7 7 Processing aid (methyl methacrylate) One One Lubricating agent (PE wax) One One UV stabilizer (benzotriazole type: hindered amine type = 70: 30% by weight) 2 2 Antioxidant (phenolic) 0.5 0.5

Table 2 below shows the performance required to be used for molding in the vehicle insulation glass and the evaluation test of the injection molded products made of the PVC composition of Example 1 and Example 2. The test methods are as shown in Table 2, and the required performances are hardness, tensile strength, elongation, hardness change after thermal aging, and melt index (M / I) required for a vehicle vehicle insulation glass molding resin.

TABLE 2

Test Items unit Performance requirements Example 1 Example 2 Test Methods Hardness 23 ℃ Shore a 80-95 85 92 ASTM D2240 80 ° C. after 1 hour 50 minimum 64 70 ASTM D2240 The tensile strength ㎏ / ㎠ 75 minimum 112 105 JIS K 6723 Elongation % 150 min 240 180 JIS K 6723 Hardness change after thermal aging (100 ℃ × 100 hours) Shore a ± 5 +2 +3 ASTM D2240 M / I (175 ℃, 5kg) g / 10min 70 minimum 88 79 ASTM D1238

As shown in Table 2, according to the polyvinyl chloride composition for vehicle encapsulation glass molding according to the present invention, after the hardness, tensile strength, elongation, heat aging required as a resin for vehicle encapsulation glass molding It satisfies all properties such as hardness change, and it can be seen that the melt index (M / I) is particularly excellent.

Although the preferred embodiment of the present invention has been described above, the present invention may use various changes, modifications, and equivalents. It is clear that the present invention can be applied in the same manner by appropriately modifying the above embodiments. Accordingly, the above description does not limit the scope of the invention as defined by the limitations of the following claims.

Claims (6)

In the polyvinyl chloride composition for vehicle encapsulation glass molding capable of low pressure injection, With respect to polyvinyl chloride (PVC) having a degree of polymerization (DP) of Degree of Polymerization (JIS K6721-77) 400 to 700 (or K value of 52 to 60, DIN 53726) and 100 parts by weight of the polyvinyl chloride; Dioctylphthalate (DOP), Diisodecylphthalate (DIDP), Diisononylphthalate (DINP), Diethylhexylphthalate (DEHP), Di-n-octylphthalate (DNOP), Dibutylphthalate (DBP), Butylbenzyl Phthalate plasticizer consisting of at least one of phthalates (BBP) and di-2-hexyl adipate (DOA), tri-ethylhexyl trimellitate (TOTM), acetyltributyl citrate (ATBC), alkyl sulfonic acids of phenol and cresol 30 to 60 parts by weight of a plasticizer composed of at least one of a nonphthalate plasticizer composed of at least one of (mesamol), diisononyl adipate (DINA), and monoglycerine; 20 to 50 parts by weight of a filler consisting of at least one of calcium carbonate, talc and mica; 3 to 8 parts by weight of a heat stabilizer made of at least one of a Sn-based heat stabilizer, a Ba-Zn-based heat stabilizer, a Ca-Zn-based heat stabilizer, a hydrotalcite-based heat stabilizer, a zeolite-based heat stabilizer, and an epoxy-based heat stabilizer; 1 to 10 parts by weight of an impact modifier including a methyl methacrylate-butadiene-styrene copolymer; 0.1 to 2 parts by weight of processing aids; 0.1 to 2 parts by weight of lubricant; 0.1-3 parts by weight of UV stabilizers; It comprises 0.1 to 1 parts by weight of antioxidant, Shore-A polyvinyl chloride composition for vehicle encapsulation glass molding, characterized in that the melt index (M / I) is 50 to 100g / min at 80 to 95, 175 ℃, 5.0kg load. delete delete delete The method of claim 1, The processing aid is methyl methacrylate, The antioxidant is at least one of divinyl benzene, triallyl cyanurate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, polyethylene glycol diketacrylate, trimethylolpropane triketacrylate, allyl methacrylate Polyvinyl chloride composition for vehicle encapsulation glass molding, characterized in that one. The method of claim 1, The UV stabilizer is a polyvinyl chloride composition for vehicle encapsulation glass molding, characterized in that at least one of a hydroxybenzophenone-based, benzotriazole-based, substituted acrylate-based, hindered amine-based ultraviolet stabilizer.