JPH022896B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a sol composition suitable for use in molding interior materials for automobiles, interior materials for ordinary homes, furniture surface materials, and the like. Conventionally, soft vinyl chloride resin has been widely used for interior materials of automobiles, such as ceilings, walls, glow box lids, rear parcels, etc. Since a plasticizer is used in soft vinyl chloride resin, a phenomenon occurs in which the plasticizer volatilizes and adheres to the glass window, causing fogging. This cloudy phenomenon is exacerbated under the scorching sun. This cloudy phenomenon is called fogging. In addition, soft vinyl chloride resin and polyurethane are often used as a composite for automobile interior materials, but in this case, vinyl chloride resin has significantly poor heat resistance and light resistance, and cracks occur during use. It is difficult to say that it exhibits sufficient performance as an interior material. The inventor of the present invention produced a vinyl chloride resin for paste using various methods, and conducted intensive studies to mold an interior material that causes less fogging, is strong even when in contact with urethane, and has excellent heat resistance and light resistance. However, during the polymerization of vinyl chloride resin, hydrogen peroxide is used as a catalyst in the presence of an anionic surfactant to polymerize, and the paste is dried while containing the anionic surfactant to produce a vinyl chloride resin for paste. By adding a specific nonionic surfactant and epoxy resin to this material and molding an interior material, the inventors discovered that the above object could be achieved and completed the present invention. That is, an object of the present invention is to provide a sol composition for molding interior materials that causes less fogging and exhibits excellent heat resistance and light resistance even when combined with urethane. Therefore, the gist of the present invention is to provide a paste prepared by aqueous emulsion polymerization or fine suspension polymerization of vinyl chloride or a mixture of vinyl chloride and a comonomer copolymerizable therewith in the presence of an anionic surfactant and a hydrogen peroxide catalyst. The present invention relates to a sol composition for interior materials containing a vinyl chloride polymer, a nonionic surfactant having a polyoxyethylene unit, an epoxy resin, and a plasticizer. To explain the present invention in detail, the vinyl chloride-based polymer is prepared by combining vinyl chloride or a mixture of vinyl chloride and a comonomer copolymerizable therewith with anionic surfactants such as fatty acid soaps, alkyl sulfates, alkylaryl sulfonates, In the presence of dialkyl sulfosuccinates, sulfated or sulfonated esters or ethers, etc., preferably having 10 carbon atoms
It is produced by aqueous emulsion polymerization or fine suspension polymerization using a hydrogen peroxide polymerization catalyst in the presence of an alkyl sulfate having ~15 alkyl groups, particularly sodium lauryl sulfate. It is desirable to use a reducing agent such as a sulfoxylate together with the hydrogen peroxide flux. The vinyl chloride polymer latex subjected to aqueous emulsion polymerization or fine suspension polymerization is dried by a method in which the anionic surfactant is contained even after drying, and the anionic surfactant is contained in the vinyl chloride polymer for paste by 0.04%. It is desirable to use a substance containing in the range of 6% by weight. When the content of anionic surfactant, especially alkyl sulfate, is less than 0.04% by weight, when a vinyl chloride polymer molded product is composited with polyurethane, the molded product will not exhibit sufficient heat resistance and light resistance. If the amount is more than 6% by weight, the heat resistance and light resistance when in contact with urethane are improved, but the surfactant tends to bleed from the molded product. Therefore, examples of comonomers copolymerizable with vinyl chloride include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl laurate;
Acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic esters such as methyl methacrylate, ethyl methacrylate, maleic esters such as dibutyl maleate, diethyl maleate, dibutyl fumarate, diethyl fumarate, etc. Fumaric acid esters, vinyl ethers such as vinyl methyl ether, vinylbutyl ether, and vinyl octyl ether, vinyl cyanides such as acrylonitrile and methacrylonitrile, α-olefins such as ethylene, propylene, and styrene, vinylidene chloride, bromide Examples include vinylidene halides and vinyl halides other than vinyl chloride such as vinyl and vinyl fluoride, and these comonomers include:
It is contained in the constituent components of the vinyl chloride polymer in an amount of 30% by weight or less, preferably 20% by weight or less. Of course, the comonomers are not limited to those mentioned above. Examples of nonionic surfactants having polyoxyethylene units include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan derivatives, etc., which may be used alone or in combination of two types. A mixture of the above is used. The amount of nonionic surfactant used is
Per 100 parts by weight of vinyl chloride polymer for paste
It is used in a range of 0.05 to 5 parts by weight, especially 0.2 to 2 parts by weight. If the amount of the nonionic surfactant used is less than 0.05 parts by weight, the vinyl chloride polymer tends to deteriorate with respect to the urethane, and the anti-fogging effect is also reduced. In addition, as the amount used increases, although good results can be obtained in terms of anti-fogging effect, the thermal stability of the vinyl chloride polymer becomes inferior, and even after taking into account the addition of heat stabilizers and processing conditions, etc. It is desirable that it be up to 100%. Unlike epoxy plasticizers such as epoxidized soybean oil, the epoxy resin used in the sol composition of the present invention is, for example, a bisphenol A type resin having two epoxy groups in the molecule, a cycloaliphatic Epoxy novolak resins, those derived from polybutadiene, or those having seven or more epoxy groups per molecule are used. The epoxy equivalent weight is generally higher than that of epoxidized soybean oil, and is generally about 100 to 1500, preferably about 150 to 700. The amount of epoxy resin used is usually 0.5 parts per 100 parts by weight of vinyl chloride polymer.
It is used in an amount of 1 to 10 parts by weight, preferably 1 to 5 parts by weight. The epoxy resin contributes to the prevention of fogging and the heat resistance and light resistance of the vinyl chloride polymer, especially when made into a urethane composite. If the amount of epoxy resin added is less than 0.5 parts by weight, it is difficult to obtain sufficiently satisfactory effects of preventing fogging, heat resistance, and light resistance. On the other hand, if it is more than 10 parts by weight, the viscosity of the sol composition becomes high. Processability deteriorates, and when molded products are formed, the epoxy resin tends to bleed, resulting in problems such as stickiness in the molded products. The plasticizer used in the sol composition of the present invention is not particularly limited as long as it is used in ordinary vinyl chloride resins, but examples include di-n-butyl phthalate, di-n-octyl phthalate, and phthalate. Acid di-
2-ethylhexyl, diisooctyl phthalate,
Octyldecyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, di-isophthalate
Phthalate plasticizers such as 2-ethylhexyl or phthalate esters of higher alcohols having about 11 to 13 carbon atoms, n-octyl-n trimellistate
-decyl, trimellitic acid plasticizers such as tri-2-ethylhexyl trimellitate, triisodecyl trimellitate, tri-n-octyl trimellitate, di-2-ethylhexyl adipate, di-n-decyl adipate, diisodecyl adipate, Fatty acid ester plasticizers such as di-2-ethylhexyl azelaate, dibutyl sebacate, di-2-ethylhexyl sebacate, tributyl phosphate, tri-2-ethylhexyl phosphate, 2-ethylhexyldiphenyl phosphate, phosphoric acid Examples include phosphate ester plasticizers such as tricresyl, epoxy plasticizers such as epoxidized soybean oil, and epoxidized tall oil fatty acid-2-ethylhexyl, and these may be used alone or in combination of two or more. In the sol composition of the present invention, a trimellitic acid plasticizer with low volatility or an ester plasticizer of higher alcohol and phthalic acid is preferred. The amount of plasticizer to be used is appropriately selected depending on the desired solid content concentration of the paste sol, fluidity, purpose of the molded product, etc., but generally it is 30 to 400 parts by weight per 100 parts by weight of the vinyl chloride polymer. parts by weight, preferably in the range from 50 to 200 parts by weight. In addition, a part of the plasticizer can be replaced with a diluent such as texanol isobutyrate or dodecylbenzene, or an organic solvent that swells the vinyl chloride polymer such as toluene or xylene. May be used. The amount of the diluent and organic solvent to be added is appropriately determined depending on the application. It is preferable to add a tin fatty acid salt to the sol composition of the present invention, whereby the anti-fogging property can be further improved. For example, tin caprate,
Various compounds such as tin laurate, tin myristate, tin palmitate, tin stearate, and maleic acid can be used, among which the alkyl group has more than 13 carbon atoms and contains free fatty acids or unreacted fatty acids. It is desirable to select an organic acid containing tin. The amount of tin fatty acid salt used is
A range of 1 to 5 parts by weight is used per 100 parts by weight. Furthermore, the sol composition of the present invention may contain additives commonly used for vinyl chloride resins.
Examples of additives include stabilizers, antioxidants, ultraviolet absorbers, fillers, colorants, etc., and these additives are often used in combination. The sol composition of the present invention is produced by adding the above-mentioned essential components or other additives as necessary and mixing them uniformly with a mixer such as a high-speed mixer or a kneader. The sol composition is then made into a molded article, for example, in the following manner. A predetermined amount of the sol composition is poured into a mold for molding the intended interior material, heated at a gelling temperature of, for example, 125 to 250°C for about 5 to 20 minutes to gel, and then cooled and the interior material is taken out from the mold. . The sol composition for interior materials of the present invention has extremely good gelling properties, probably because it uses a hydrogen peroxide catalyst for the vinyl chloride polymer, and can be processed by reducing the viscosity by adding a nonionic surfactant. Excellent sex,
The molded products obtained from this are strong and, even when used as parts for automobiles, the fogging phenomenon caused by volatilization of the plasticizer is significantly reduced. In addition, even when used as a composite with urethane resin, it is not affected by isocyanate or freon used as a foaming agent for urethane, exhibits excellent heat resistance and light resistance, and can be used for a long period of time. can. Therefore, the sol composition of the present invention can be used for ceiling materials, wall materials, glow box lids, rear parcels, armrests, headrests, etc. of vehicles, wall materials, ceiling materials, floor materials, etc. of ordinary homes, furniture, etc. It can be used extremely effectively as a surface material. The present invention will be described in detail below with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. In addition, "parts" in the examples indicate "parts by weight." Example 1 Vinyl chloride polymer for paste (degree of polymerization 1500)
100 parts (polymerization under hydrogen peroxide catalyst, emulsifier sodium lauryl sulfate 2% by weight) tri-2-ethylhexyl trimellitate 70 parts tin stearate 3 parts epoxy resin (bisphenol A type) 5 parts pigment small amount polyoxyethylene octylphenyl ether
Predetermined amount A paste-sol composition having the above-mentioned composition is poured into a mold for an automobile meter hood with varying amounts of polyoxyethylene octyl phenyl ether, heated and rotationally molded at 180°C for about 10 minutes, then cooled and molded. The product was taken out and a molded interior material for an automobile's meter hood was obtained. A urethane resin was injected into the vinyl chloride resin molded product and foamed (freon foaming of polyol and polyisocyanate) to obtain a composite. The fogging property of the molded article and the heat resistance of the composite were tested. The fogging property and heat resistance tests were conducted as follows. <Fogging property> Place the interior material 50mm x 100mm x 1mm in a wide mouth bottle,
The opening of the wide-mouth bottle was covered with a transparent glass plate. This was kept in an oil bath at 80°C for 20 hours, and the degree of cloudiness of the transparent glass plate was measured using an integrating sphere photometer. (Japanese Automobile Standards). <Heat resistance> The test piece after the urethane composite was placed in a gear oven at 110°C, and the time until it turned brown was measured.

[Table] Example 2 Vinyl chloride polymer (same as Example 1)
100 parts diisodecyl phthalate 70 parts tin stearate 3 parts epoxy resin 4 parts pigment Small amount of polyoxyethylene octyl phenyl ether
0.5 parts A predetermined amount of the above sol composition was poured into an automobile armrest mold, and rotational molding was performed at 190° C. for about 5 minutes. This was subjected to fogging property and heat resistance tests (80°C) in the same manner as in Example 1, and the results are shown below. Fogging value 2.8% Heat resistance test No abnormalities after 400 hours. Example 3 In Example 1, the nonionic surfactant was added to 0.5
A urethane heat resistance test was conducted by varying the amount of epoxy resin added. The results are shown in Table 2.

[Table] Comparative Example The same test as in Example 1 was conducted using a similar formulation as in Example 1 (see Table 3).

【table】

Claims (1)

[Scope of Claims] 1 Vinyl chloride for paste obtained by aqueous emulsion polymerization or fine suspension polymerization of vinyl chloride or a mixture of vinyl chloride and a comonomer copolymerizable with vinyl chloride in the presence of an anionic surfactant and a hydrogen peroxide catalyst. A sol composition for interior materials, comprising a polyoxyethylene polymer, a nonionic surfactant having a polyoxyethylene unit, an epoxy resin, and a plasticizer. 2. The sol composition for interior materials according to claim 1, wherein the anionic surfactant is an alkyl sodium sulfate.