JPS6333485B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides, for example, a surface treatment agent for an inorganic filler,
Dispersants, interlining adhesives, powder coatings, paint additives,
The present invention relates to a silane-modified wax that can be post-crosslinked and exhibits unique properties for use as a compounding agent in other resins, molded products, etc., and a method for producing the same. More specifically, in the present invention, the intrinsic viscosity "η" is
A graft copolymer of wax a of 0.05 to 0.8 and a silane compound b having a group having an olefinic unsaturated bond and a hydrolyzable organic group, and the amount of the grafted silane compound b is It relates to a silane-modified wax characterized in that it is 0.3 to 45% by weight and has an intrinsic viscosity "η" of 0.05 to 0.85. The present invention also relates to a method for producing such a silane-modified wax, in particular when the intrinsic viscosity "η" is 0.05.
~0.8 wax a and a silane compound b having a group having an olefinic unsaturated bond and a hydrolyzable organic group are reacted under non-extrusion molding reaction conditions in the presence of a radical initiator. The present invention also relates to a method for producing the above-mentioned silane-modified wax. Traditionally, post-crosslinkable silane-modified plastics,
Numerous proposals are known regarding their preparation and use. However, conventional proposals commonly focus only on silane modification that allows for post-crosslinking of plastics or elastomers.
There has never been any mention of silane modification of waxes. This is natural considering the inherent utility value of wax, but until now there has been no idea to provide wax itself with crosslinking properties. In addition, in the field of silane-modified plastics that can be post-crosslinked, there is a need to apply the above-mentioned modification means to waxes whose fields of use and properties are significantly different from those of plastics. There was never any expectation or suggestion that any benefit might be obtained. Regarding the above-mentioned post-crosslinkable silane-modified plastics, for example, Japanese Patent Publication No. 1711/1983 describes that plastics made of ethylene polymers or copolymers contain a group having an olefinic unsaturated bond and a hydrolyzable organic A method of grafting a silane compound having a group and crosslinking the silane-modified plastic is disclosed. However, nowhere in this proposal is there any mention of modification of waxes such as ethylene-based synthetic waxes. Regarding similar post-crosslinkable silane-modified plastics, their preparation and use,
JP-A-50-138042, JP-A-51-48791, JP-A-51-102039, JP-A-51-19459, JP-A-52
-9054, JP-A-52-44864, JP-A-52-40555
No., JP-A-52-33938, JP-A-52-154872,
Proposals such as JP-A No. 52-155385 are also known, but as mentioned above, the conventional proposals commonly disclose only silane modification that can be post-crosslinked for plastics or elastomers, and only for waxes. No technical ideas or proposals regarding modification are disclosed. In such disclosed post-crosslinkable silane-modified plastics, it is technically difficult to efficiently and uniformly graft an expensive silane compound in an industrially advantageous manner; The grafting reaction is preferably carried out continuously in an extruder, and the amount of silane compound grafted is also limited due to residence time, resulting in a high grafting yield (ratio of monomer grafted to wax to monomer charged). It is also difficult to graft silane compounds. The present inventors have been conducting research on silane modification and post-crosslinking physical properties of waxes based on a completely different idea. As a result, it has been discovered that a silane-modified product of waxes, which has never been proposed before, can be provided by easy means and exhibits unexpected and remarkable unique usefulness. As a result of further research, the intrinsic viscosity [η] defined later
0.05 to 0.8, preferably about 0.05 to 0.6, and a silane compound having a group having an olefinic unsaturated bond and a hydrolyzable organic group; It is possible to provide a silane-modified wax with a grafting amount of silane compound b (silane compound content) of 0.3 to 45% by weight at a high yield, and that this silane-modified wax has extremely useful and unique improvements over unmodified wax. Furthermore, the silane-modified wax with the grafting amount of the silane compound of 0.3 to 45% by weight, particularly 5 to 40% by weight, is one of the known modified waxes. It has been discovered that the modified wax after post-crosslinking has higher fluidity than silane-modified plastics and has unexpectedly excellent properties in terms of solvent resistance, heat resistance, adhesion, and non-dripability during combustion. Furthermore, this silane-modified wax has unique physical properties different from conventionally known silane-modified plastics and elastomers, as it has suitability for non-pressure casting at 80 to 160°C, which will be described later, when used in the molding field. It was found to be a modified product. Furthermore, this silane-modified wax can be produced by, for example, combining the above-mentioned wax a and the above-mentioned silane compound b in the presence of a radical initiator under non-extrusion molding reaction conditions, and by further selecting the reaction conditions, a high grafting yield,
For example, it has been found that it is possible to produce a homogeneous grafted modified product with a high content of silane compounds grafted onto 95% wax. Therefore, an object of the present invention is to provide a silane-modified wax which has not been described in any literature. Another object of the present invention is to provide an industrially advantageous method for producing a silane-modified wax having the above characteristics. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. The wax used as a raw material in the present invention has an intrinsic viscosity (solvent decalin, temperature 135°C) of 0.05 to 0.8.
It is within the range of . If it is less than 0.05, the hardness, strength, etc. of the silane-modified wax obtained will be insufficient even if the grafting ratio of the silane compound is increased. Further, if the intrinsic viscosity exceeds 0.8, the melt viscosity becomes high, making it unsuitable for purposes such as non-pressure casting. If you intentionally heat it to a high temperature to achieve a viscosity that is suitable for work, the heat cycle will become longer,
In addition to disadvantages in terms of productivity and cost, such as the need for a large amount of thermal energy, it is also undesirable because of the quality of the molded product, such as oxidative deterioration or deterioration of the wax, and dimensional stability. These waxes include, for example, natural waxes such as paraffin waxes and microcrystalline waxes, and synthetic waxes such as Fischer-Tropsch synthetic waxes and polyolefin waxes, among which polyolefin waxes are preferred. Polyolefin waxes include one or more polymers such as ethylene, propylene, 1-butene, 1-pentene, and 4-methyl-1-pentene, such as polyethylene waxes and ethylene-propylene copolymers. wax, poly-1-butene wax, poly-4-methyl-1-pentene wax, 4-methyl-1-pentene-1-decene copolymer wax, as well as ethylene and α,β unsaturated carboxylic acid or its derivatives. copolymers such as ethylene/vinyl acetate copolymer wax, ethylene/acrylic acid copolymer wax, ethylene/vinyl acetate copolymer wax,
Examples include ethyl acrylate copolymer wax and ethylene/maleic anhydride copolymer wax. These waxes are partially or completely chlorinated,
It also includes waxes to which α,β-unsaturated carboxylic acids, alicyclic carboxylic acids, etc., or derivatives thereof such as esters, amides, imides, anhydrides, metal salts, etc. are grafted in advance. These polyolefin waxes include those obtained by direct polymerization using Ziegler type catalysts and radical initiators, as well as polyolefin waxes obtained by thermally decomposing high molecular weight polyolefin resins or degrading them by other methods. be. In particular, waxes obtained by direct polymerization with Ziegler type catalysts and radical initiators, hydrogenated products of thermally decomposed waxes, etc.
Materials with a low degree of unsaturation are suitable. The wax preferably used in the present invention has [η] in a range of 0.05 to 0.6, and the silane-modified wax produced therefrom has a penetration degree (JiS-K-2350) of 0 to 50. , and 160
It has a melt viscosity of 1 to 300,000 cps at a temperature of 1 to 300,000 cps and a non-pressure casting suitability of 80 to 160 degrees Celsius. The silane compound grafted onto the wax may be a silane compound having a group having an olefinic unsaturated bond and a hydrolyzable organic group,
General formula R ¹ R ² SiY ¹ Y ² , R ¹ XSiY ¹ Y ² or R ¹ SiY ¹ Y ² Y ³
It is indicated by. In the formula, R ¹ and R ² have an olefinic unsaturated bond, are composed of carbon, hydrogen and optionally oxygen, are the same or different groups, and are reactive with the free radical site generated in the polyolefin. Examples of such groups include vinyl, allyl, butenyl, cyclohexenyl, and cyclopentadienyl, with terminal olefinically unsaturated groups being particularly preferred. Other preferred examples include CH ₂ =C(CH ₃ ) having an ester bond of a terminal unsaturated acid;
COO( _CH2 ) _3- , _CH2 =C( _CH3 )COO( _CH2 ) _2-
O-( _CH2 ) _3- , _CH2 =C( _CH3 )
Examples include COOCH ₂ OCH ₂ CH ₂ (OH)CH ₂ O(CH ₂ ) ₃ −. Among these, vinyl groups are most suitable. X is an organic group having no olefinic unsaturated bond, such as monovalent hydrocarbon groups such as methyl, ethyl, propyl, tetradecyl, octadecyl, phenyl, benzyl, tolyl, etc. , or a halogen-substituted hydrocarbon group. The groups Y ¹ , Y ² , Y ³ are each the same or different hydrolyzable groups, such as alkoxy groups such as methoxy, ethoxy, butoxy, methoxyethoxy, alkoxyalkoxy groups, formyloxy, acetoxy, propionoxy, etc. Acyloxy group, oxime e.g. -ON=C
(CH ₃ ) ₂ , −ON=CHCH ₂ C ₂ H ₅ and −ON=C
( _C6H5 ) ₂ or substituted amino groups and arylamino groups, such _{as -NHCH3} , _{-NHC2H5 and} -
NH (C ₆ H ₅ ), etc., and any other hydrolyzable organic group. The silane compound preferably used in the present invention is a compound represented by the general formula R ¹ SiY ¹ Y ² Y ³ , in particular the groups Y ¹ , Y ² ,
Silane compounds with equal Y ³ are suitable. Among these, vinyltris alkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris(methoxyethoxy)silane are most suitable. However, vinylmethyldiethoxysilane, vinylphenyldimethoxysilane, etc. can be used as well. Grafting of the silane compound onto the wax is carried out by reacting the wax and the silane compound under non-extrusion reaction conditions in the presence of a radical initiator in an inert gas atmosphere in the absence of oxygen. That is, no extruder is required for grafting. In order to uniformly graft the silane compound, the graft reaction is usually carried out using a reactor. The graft reaction is preferably carried out by heating the wax and stirring vigorously. The reaction temperature is preferably 300°C above the melting point of the wax, particularly in the range of about 140°C to 200°C, and the reaction time is usually 1 to 20 hours. The reaction may be carried out in either a batch or continuous manner, but the batch method is preferred in order to achieve uniform grafting and to obtain good crosslinking properties. In the present invention, it is preferable to carry out the graft reaction while sequentially adding the silane compound to the wax. Further, it is preferable to add the radical initiator simultaneously and sequentially. Specifically, the addition rate of the silane compound is preferably 0.1mM to 10mM/min/Kg-wax, particularly 0.5mM to 5mM/min/Kg-wax.
min/Kg-wax is preferred. This reaction method allows for homogeneous grafting onto wax molecules with a high grafting yield (ratio of the amount of grafted monomer to the amount of monomer charged), and the formation of a homopolymer of the silane compound is extremely suppressed. It can be used for normal purposes simply by removing volatile components such as a small amount of unreacted monomers, radical initiators, and their decomposition products under vacuum, and can be used for dissolving and dissolving.
Purification steps such as precipitation and extraction that increase production costs can be omitted. In addition, this reaction method is suitable for obtaining a homogeneous silane-modified wax that has a high content of the grafted silane compound, specifically, a grafted amount of 3 to 40% by weight, and is colorless and transparent without clouding when melted. Wax is particularly excellent in solvent resistance, heat resistance, adhesion, and non-dripability during combustion after water crosslinking. The amount of silane compound and radical initiator added to the wax can be varied within a wide range depending on the type of wax, reaction temperature, and desired degree of crosslinking. A suitable range is 0.5 to 100 parts by weight of the silane compound, particularly about 5 to 100 parts by weight, per 100 parts by weight of wax.
50 parts by weight and 0.01 to 10 parts by weight of radical initiator, especially about 0.03 to 5 parts by weight. In addition, the molar ratio of the radical initiator to the silane compound is set to 1/
200 to 1, preferably 1/100 to 1/5. As the radical initiator, one that can create radical sites in the wax under silane modification reaction conditions is used. These compounds include organic peroxides, organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide,
Dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxybenzoate) hexyne-3,1,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl Peracetate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,
5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert
-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate, other azo compounds such as azobis-isobutylnitrile, dimethylazoisobutyrate There is. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(tert- Dialkyl peroxides such as butylperoxy)hexane and 1,4-bis(tert-butylperoxyisopropyl)benzene are preferred. During the graft reaction, an antioxidant can be added to the wax in advance. For example, add a known antioxidant to 100 parts by weight of wax.
It is used in an amount of 0.005 to 10% by weight.
These antioxidants may be added and uniformly mixed together with a silane compound, a radical catalyst, and other additives as necessary. Antioxidants suitably used in the present invention include known radical inhibitors, with phenol compounds or amine compounds being particularly preferred;
For example, (a) monophenolic compounds, (b) bis, tris, or polyphenolic compounds, (c) thiobisphenol compounds, and (d) polyphenolic compounds and (e) naphthylamine compounds; (f) It is selected from amine compounds consisting of diphenylamine compounds or (H)p-phenylenediamine compounds. Compounds having a 2,6-dimethylpiperidine skeleton are also effective. (a) Compounds belonging to monophenolic compounds include 2,6-di-tert-butyl-p-cresol,
2,6-di-tert-butylphenol, 2,4-
Dimethyl-6-tert-butylphenol, 2-methyl-4,6-di-nonylphenol, butyl
hydroxyanisole, styrenated phenol,
2,4,6-tri-tert-butylphenol, n
-octadecyl-3-(4'-hydroxy-3',5'-
di-tert-butylphenol) propionate. (b) Bis, tris or polyphenol compounds include 4,4-dihydroxydiphenyl,
2,2'-methylenebis(4-methyl-6-tert-
butylphenol), 2,2'-methylenebis(4
-ethyl-6-tert-butylphenol), 2,
2'-methylenebis(4-methyl-6-cyclohexylphenol), 4,4'-methylenebis(2,
6-di-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2'-dihydroxy-
3,3'-di(α-methylcyclohexyl)-5,
5'-dimethyl diphenylmethane, 1,3,5-
Trimethyl-2,4,6-tris(3,5-di-
tert-butyl-4-hydroxybenzyl)benzene, tris(2-methyl-4-hydroxy-5-
tert-butylphenyl)butane, tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane. (c) Thiobisphenol compounds include 4,4'-
Thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-o
-cresol), 2,2'-thiobis(6-tert-butyl-4-methylphenol) and (d) polyhydric phenol or its derivatives include 2,5-di-tert-butylhydroquinone, hydroquinone monomethyl ether, Examples include 2,5-di-(tertiary amyl)hydroquinone. (e) Naphthylamine compounds include phenyl-α-naphthylamine, phenyl-β-naphthylamine, and aldol-α-naphthylamine; (f) diphenylamine compounds include p-isopropoxydiphenylamine and p-(p-toluene).・Sulfonylamide)-diphenylamine, bis(phenyl isopropylidene)-4,4'-diphenylamine, N,N'-diphenyl ethylenediamine, N,N'-diphenyl propylenediamine, and (H) p-phenylene. Diamine compounds include N,N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-
p-phenylenediamine, N,N'-di-(2-naphthyl)-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N,N'-bis(1-methyl heptyl)-p
-phenylenediamine, N,N'-bis(1,4
-dimethylpentyl)-p-phenylenediamine,
Examples include N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine. Among the above radical inhibitors, those that have good compatibility with wax, good color of the product, and are easy to handle are preferred, and among them, the phenolic radical inhibitors (a), (b), and (c) are particularly preferred. When the phenolic radical inhibitors (a) and (b) and the thiobisphenol radical inhibitor (c) are used in combination, heat resistance can be imparted to the wax. The amount of antioxidant added varies depending on the wax used, the type and amount of radical initiator used, the reaction conditions, and the type of antioxidant, and is selected so as not to completely lose the action of the radical initiator. Generally, 0.01 to 3 parts by weight, particularly 0.03 to 1 part by weight per 100 parts by weight of wax is suitable. In addition, when blending with a radical crosslinkable polymer, it generally varies from 0.02 to 1 of the amount of the radical initiator, although it varies depending on the type of polymer.
Blending in twice the amount prevents gelation or decomposition during the grafting reaction, and is preferable from a work standpoint. The silane-modified wax of the present invention is obtained by graft-copolymerizing a silane compound to wax, and the proportion (grafting amount) of the silane compound in the silane-modified wax is in the range of 0.3 to 45% by weight. 0.3% by weight
If it is less than that, there is almost no difference from unmodified wax. If the content exceeds 45% by weight, the excellent performance of the silane-modified wax may remain unchanged or begin to deteriorate. That is, even if a large amount of an expensive silane compound is used, economical efficiency and productivity deteriorate, and melt fluidity is impaired. Therefore, even in a silane-modified wax, the grafting amount of the silane compound is 0.3 to 45% by weight, especially 3 to 40% by weight.
The range of weight% is economical, productivity, physical properties,
For example, it is recommended from the viewpoints of compatibility, melt flow characteristics, and when molded into a molded product, solvent resistance after post-crosslinking, heat resistance, adhesion, creep resistance, and non-dripability during combustion. The physical properties of such a silane-modified wax include a penetration degree (JIS-K-2350) of 0 to 50, particularly about 5 to 40.
and the melt viscosity at 160℃ is 10,000 to 300,000
The preferred range is cps, particularly about 100,000 to 50,000 cps. The silane-modified wax of the present invention takes advantage of its fluidity and can be easily cast into a mold by heating and melting it at a temperature slightly higher than its melting point or by simply applying a little pressure. By processing, it is possible to obtain complex molded products with excellent strength, heat resistance, solvent resistance, adhesion, creep resistance, and low heating drop resistance. In other words, the silane-modified wax of the present invention has a suitability for non-pressure casting of 80% as determined by the test method described later.
It was found that the temperature was ~160°C. The crosslinking treatment can be carried out at any stage.
For example, if water is introduced into the grafted silane compound while the molded article is in the presence of a silanol condensation catalyst, a crosslinking reaction will take place and cross-bond with each other, improving the performance of the molded article. The contact with moisture takes place with water in various states, including humidity, water baths, hot water baths, steam, etc. Further, the silanol condensation catalyst only needs to be present at least during the crosslinking treatment. Therefore, the silanol catalyst may be dissolved or suspended in the water, and if necessary, the silane compound may be added to the wax after grafting before or during grafting. The addition may be carried out simultaneously with other additives, such as antioxidants, or
A masterbatch of wax to which a silanol condensation catalyst has been added may also be used. The silanol condensation catalyst used in the present invention includes dibutyltin dilaurate, stannous acetate, stannous octoate (stannous caprylate) + tin naphthenate, zinc caprylate, iron 2-ethylhexanoate, and naphthenic acid. Organometallic compounds such as cobalt carboxylates, titanate esters and chelates, such as titanate tetrabutyl ester, titanate tetranonyl ester and bis(acetylacetonitrile) di-isopropyl titanate,
These include organic bases such as ethylamine, hexylamine, dibutylamine and pyridine, and acids such as fatty acids. Among these, organic tin compounds, particularly tin carboxylates such as dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin dioctate are preferred. In the present invention, as an embodiment, after molding,
Gradual crosslinking treatment can also be carried out by leaving the material in the air without exposing it to moisture, using the moisture in the air. The silane-modified wax of the present invention may contain additives such as clay, calcium carbonate, calcium silicate, kaolin, and talc before, during, or after grafting the silane compound to the extent that its fluidity is not impaired. , silica, diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fibers, glass bulbs, glass balloons, carbon fibers or colorants, e.g. Carbon black, titanium oxide, zinc white, red iron, ultramarine blue, azo pigments, nitroso pigments, lake pigments, phthalocyanine pigments, and blowing agents such as azodicarbonamide, dinitrosopentamethylenetetramine, p,p'-oxybisbenzenesulfate. Heat-activated nitrogen generating substances such as fonyl hydrazide and N,N'-dimethyl-N,N'-dinitrosoterephthalamide, and carbon dioxide releasing blowing agents such as sodium bicarbonate and ammonium carbonate can be incorporated. Also other additives, such as process oils, plasticizers, lubricants,
Voltage stabilizers, ultraviolet absorbers, etc. are added as necessary. Additives that are preferably added in the present invention include moisture-releasing additives that release moisture at a certain temperature or higher, for example, at a molding temperature or higher.
Examples of such materials include alumina, porous materials such as molecular sieves that have water adsorbed, gypsum, aluminum hydroxide, and other water-eliminating organic compounds such as vinyl alcohol. , polyvinyl alcohol, dicarboxylic acids such as maleic acid, β-hydroxy-carboxylic acids, and derivatives thereof. These water-releasing additives are preferable because they enable uniform crosslinking of molded articles. Also other base materials,
For example, adhesive strength can be improved because it can be bonded to metals such as aluminum and copper, resins, or even the interface of laminated parts can be uniformly crosslinked. These moisture-releasing additives usually release moisture during hot molding, but they may also be ones that do not release moisture during molding and only slowly release moisture when left in the air after molding. Also used are hygroscopic compounds that do not contain water during molding and easily absorb moisture after molding. The molded product after crosslinking treatment not only has excellent strength, but also excellent solvent resistance, heat resistance, adhesion, and resistance to combustion and dripping. The timing of crosslinking treatment of the silane-modified wax of the present invention can be arbitrarily selected. Furthermore, before crosslinking treatment, it can be used for various purposes utilizing its compatibility and flow characteristics, and can be added to various resins to improve their performance. The uses of silane-modified wax are shown below. When glass fibers coated with the silane-modified wax of the present invention or inorganic fillers such as calcium carbonate are added to resins such as polyethylene, polypropylene, polyethylene terephthalate, and polytetramethylene terephthalate, they exhibit excellent adhesion to the resin, strength, and warpage. It is possible to improve preventive properties. The blending amount is preferably 1 to 99% by weight. The silane-modified wax of the present invention can be applied to various substrates, such as films such as polyethylene film and polypropylene film, cardboard, woven fabrics, non-woven fabrics, cellulose films such as cellophane, aluminum,
The adhesion between these base materials can be improved by coating metal plates such as copper and tin using a solution method, a melting method, a powder coating method, or the like. Furthermore, in order to improve the adhesion of ink, paint, etc. to polyolefin molded products, the molded products can be coated in advance with the silane-modified wax of the present invention. When coating an electric wire with a polyethylene resin, the electric wire can be coated with the silane-modified wax of the present invention in advance to improve the adhesion between the electric wire and the resin. Woven fabrics, nonwoven fabrics, paper, and mixed paper can be impregnated and crosslinked with the silane-modified wax of the present invention to perform water-repellent treatment. It can also be an electrical insulator. The silane-modified wax of the present invention can be used as an adhesive with excellent organic solvent resistance (percrene resistance, etc.) for woven fabrics and nonwoven fabrics. An example is interlining adhesive. When the silane-modified wax of the present invention is used as an adhesive, ethylene-vinyl acetate copolymer, ethylene-alkyl methacrylate copolymer, ethylene-alkyl acrylate copolymer, and partially hydrolyzed products thereof may be added to the silane-modified wax. , synthetic rubber can be added to improve high temperature adhesion. The proportion of silane-modified wax is preferably 1 to 99% by weight. The surfaces of metal cans and metal pipes can be powder coated with the powdered silane-modified wax of the present invention. By adding the silane-modified wax of the present invention to a paint, it is possible to improve the adhesion to the painted surface and the water resistance, heat resistance, and solvent resistance of the paint film. It can also be added to traffic paints to improve workability and impart weather resistance and stain resistance to the paint film. When metal fibers, glass fibers, or plastic fibers whose surfaces are coated with the silane-modified wax of the present invention are added to mortar, plaster, concrete, etc., crosslinking is performed by water during curing or curing, resulting in improved strength. At the same time, deterioration of the fiber due to an alkaline atmosphere can be prevented. The silane-modified wax of the present invention is made of polyethylene,
Post-crosslinked molded products obtained by adding it to plastics such as polypropylene can improve heat resistance, solvent resistance, stress crack resistance, and cleaving resistance. The blending amount is 1-99wt%
is suitable. The silane-modified wax of the present invention can be added to a polyolefin film to improve its gas barrier properties. The blending amount is preferably 1 to 99% by weight. When the silane-modified wax of the present invention is added and post-crosslinked when molding a polyolefin gasoline tank, a gasoline tank with improved solvent resistance can be obtained. In addition, the silane-modified wax of the present invention can be used as a mold release agent for shell molds. Examples are shown below. However, each measurement method was as follows. Γ Intrinsic viscosity [η] Determined from the value measured at 135°C using decalin as a solvent. Γ Penetration JIS-K-2350 Γ Melt viscosity Measurement was performed at 160°C using a B-type viscometer. Γ Suitability for non-pressure casting molding Heat the sample and pour it into the copper mold (inner diameter (D) 5 mm, depth (H) 10 cm) shown in Figures 1 and 2 to fill the mold, cool it, The minimum heating temperature (°C) of the sample at which a dense cast product with no voids can be obtained after taking out the cast product is shown. However, the temperature of the copper mold shall be measured at 60°C if the heating temperature of the sample is 100°C or less, and 80°C if the heating temperature of the sample exceeds 100°C. Example 1 (Production of silane-modified wax) Polyethylene wax ([η] = 0.24, density 0.97
g/cc, melt viscosity 370 cps (160°C)) was charged into a glass reactor with a capacity of 2000 c.c. Next, heat the polyethylene wax to 150℃,
After purging the system with nitrogen, add a silane compound and di-tert-butyl peroxide as a radical initiator while rotating the stirring blade at 600 times/min. Vinyltrimethoxysilane 0.80 g/min Di-tert-butyl peroxide
The addition was completed in 4 hours at a rate of 0.0225 g/min, and the reaction was continued for an additional hour. After keeping the inside of the system under a vacuum of 5 Torr for 1 hour, it was taken out into a vat and cooled to room temperature to obtain 1160 g of silane-modified wax. The total amount added was 192 g vinyltrimethoxysilane and 5.41 g di-tert-butyl peroxide. The obtained silane-modified wax was colorless and transparent when melted, the amount of grafting was 15.2% by weight, and the grafting yield was
92.8%, the intrinsic viscosity was 0.26, the penetration was 2, and the melt viscosity was 410 cps. In addition, the suitability for non-pressure casting molding was 145°C. Example 2 The procedure of Example 1 was repeated except that the total amount of the silane compound and radical initiator were added at once, and 1075 g of silane-modified wax was obtained. The obtained silane-modified wax was cloudy when heated and melted, the amount of grafting was 6.8% by weight, the grafting yield was 38.5%, the intrinsic viscosity was 0.27, the penetration was 2, and the melt viscosity was 420. In addition, the suitability for non-pressure casting molding was 145°C. Example 3 In Example 1, the radical initiator di-tert-
The reaction was carried out in the same manner except that 40 g of butyl peroxide was used and the stirring blade was rotated 400 times/min during the reaction.
1095g of modified wax was obtained. The obtained silane-modified wax is colorless and transparent when melted, the amount of grafting is 14.9wt%, the grafting yield is 85%, the intrinsic viscosity is [η] = 0.28, the penetration is 6, and the amount of grafting is 14.9wt%. The viscosity was 800 cps. Moreover, the suitability for non-pressure casting molding of this material was 150°C. Example 4 Polyethylene wax ([η] = 0.3, melt viscosity
3200 cps (160°C)) was charged into a glass reactor with a capacity of 2000 c.c. Next, apply polyethylene wax.
After heating to 165℃ and replacing the system with nitrogen, the stirring blade was heated to 600℃.
0.34g/min di-tert-butyl peroxide and silane compound and peroxide as a radical initiator while rotating
Addition was completed in 4 hours at a rate of 0.0096 g/min, and the reaction was continued for an additional hour. Furthermore, after keeping the inside of the system at 5 Torr vacuum for 1 hour, it was taken out into a vat and cooled to room temperature.
A silane-modified wax of g was obtained. The total amount added was 82.2 g vinyltrimethoxysilane and 2.3 g di-tert-butyl peroxide. The obtained silane-modified wax was colorless and transparent when melted, the amount of grafting was 6.7% by weight, and the grafting yield was 84%. Further, the intrinsic viscosity [η] of the silane-modified wax was 0.35. Example 5 0.1 phr of dibutyltin dilaurate was added to the silane-modified waxes obtained in Examples 1, 2 and 3,
After heating and melting at 160℃, it is cast onto a room temperature iron plate.
A sheet with an average thickness of 0.8 mm was molded. This sheet was immersed in a 60°C water bath for 24 hours to perform crosslinking treatment. Table 1 shows the physical properties after crosslinking treatment.

[Table] Comparative Example 1 A sheet made from unmodified polyethylene wax, the raw material used in Examples 1 and 2, by the method of Example 5 cracked when cooled and fell apart, making physical property tests impossible. It was hot. Comparative example 2 High density polyethylene (Mv=500000, density 0.968
g/cc) 1000g of radical initiator dicumyl peroxide 1.2g and vinyltrimethoxysilane 30g
After mixing g, Sunnox R2g, and calcium stearate 1.5g in a Henschel mixer, use a 20mm granulator to set the barrel temperature C ₁ /C ₂ /D = 200 /
The reaction was carried out at 220/220°C to obtain 1005g of silane-modified polyethylene resin. As a result of analysis of the product, the amount of grafting was 1.22% by weight, and the grafting yield was 40.9%. This silane-modified product was press-molded (200°C) into a sheet with a thickness of 1 mm. 60 sheets of this
It was immersed in a water bath at ℃ for 24 hours to perform crosslinking treatment. The dripping property of the crosslinked product during combustion was "dripping". Example 6 (Low-pressure injection molding) 0.5 phr of dibutyltin dilaurylate was added to the silane-modified wax obtained in Example 4, the nozzle temperature of the injection molding machine was set at 135°C, and the mold was molded to a thickness of 2 mm at room temperature. A square plate was formed. Hold this square plate at 90℃
It was immersed in a water bath for 17 hours to perform crosslinking treatment. Table 2 shows the physical properties of the crosslinked product.

[Table] Comparative Example 3 The raw material unmodified wax used in Example 4 was subjected to low-pressure injection molding in the same manner as in Example 6. The formed square plate cracked as soon as it was taken out of the mold, fell apart and could not maintain its shape. Comparative Example 4 After washing the surface of the sheet obtained in Example 5 (Examples 1 and 3) with methanol and drying, the transparent silicone resin for hard coating X manufactured by Shin-Etsu Silicone was applied.
-12-921 was applied and heat treated at 80°C for 3 hours. When this item was subjected to a goban eye test,
It was 100/100. The silane-modified product obtained in Comparative Example 3 was formed into a 0.8 mm sheet using a press molding machine, and then applied and heat treated in the same manner as described above, but the grain test of this product was 0/100. It was hot. Comparative Example 5 In Example 1, high density polyethylene (Mv=500000, density 0.968
The reaction was carried out in the same manner as in Example 1, except that the reaction temperature was changed to 220°C. However, due to the high melt viscosity, it took about 15 minutes after starting the addition of the silane compound and radical initiator. However, stirring became impossible and the stirring motor stopped due to overload. Example 7 The silane-modified wax obtained in Example 1 was charged into a glass reaction vessel equipped with a stirrer and a cooler, and the solid content was heated to 80°C with toluene.
A 20wt% solution was prepared. This product remained a transparent liquid even at room temperature. This solution was applied to an injection square plate obtained from a polypropylene block copolymer with a melt flow ratio (ASTMD1238) of 8.0 g/10 min.
After cleaning with 1,1-trichloroethane vapor for 30 seconds, apply with air spray, approximately 10μ (when dry)
An undercoat film was prepared. After leaving this test piece in an oven at 60℃ and 95% relative humidity for 24 hours, the moisture on the surface was removed by air blowing, and an amino alkyd paint was applied so that the dry film thickness was 40μ.
Baking was performed at 140°C for 40 minutes. Adhesion of the resulting coating film (Goban test JIS
K5400) and surface gloss (JIS K-5400) were measured. The results are shown in Table 3. Comparative Example 6 A sample was prepared in the same manner as in Example 7, except that the silane-modified polyethylene resin obtained in Comparative Example 2 was used, and the physical properties were measured. The results are shown in Table 3. The 20 wt % toluene solution of this modified resin was opaque at room temperature and the resin was not completely dissolved.

【table】 [Brief explanation of drawings]

FIGS. 1 and 2 are a perspective view and a cross-sectional view of a mold used for testing suitability for non-pressure casting molding.

Claims (1)

[Claims] 1. Wax a having an intrinsic viscosity "η" of 0.05 to 0.8;
A graft copolymer with a silane compound b having a group having an olefinic unsaturated bond and a hydrolyzable organic group, and the amount of the grafted silane compound b is 0.3 to 45% by weight,
and a silane-modified wax characterized by an intrinsic viscosity "η" of 0.05 to 0.85. 2 Penetration of the silane-modified wax (JIS-K-
2350) is 0 to 50, and has a melt viscosity of 1 to 300,000 cps at 160°C. 3. The silane-modified wax according to claim 1, wherein the silane-modified wax has suitability for non-pressure casting at 80 to 160°C. 4 Wax a with an intrinsic viscosity "η" of 0.05 to 0.8,
The above a and b are characterized in that the silane compound b having a group having an olefinic unsaturated bond and a hydrolyzable organic group are reacted under non-extrusion molding reaction conditions in the presence of a radical initiator. A method for producing a silane-modified wax which is a graft copolymer, has a grafting amount of the grafted silane compound b of 0.3 to 45% by weight, and has an intrinsic viscosity "η" of 0.05 to 0.85. 5. The manufacturing method according to claim 4, wherein the reaction is carried out while sequentially adding the silane compound b. 6 Addition rate of the silane compound b from 0.1 to
The manufacturing method according to claim 4, characterized in that the wax is 10mM/min/Kg. 7 Penetration of the silane-modified wax (JIS-K-
2350) is 0 to 50, and the melt viscosity at 160°C is 1 to 300,000 cps. 8. The manufacturing method according to claim 4, wherein the silane-modified wax has suitability for non-pressure casting at 80 to 160°C. 9. For 100 parts by weight of wax a, 0.5 to 100 parts by weight of silane compound b and 0.01 to 10 parts by weight of radical initiator.
The manufacturing method according to claim 4, characterized in that part by weight is added. 10. The manufacturing method according to claim 9, wherein the amount of the radical initiator added is 1/200 to 1 in molar ratio to the silane compound b. 11 A manufacturing method in which an antioxidant is further added to wax A, in which the amount of the antioxidant is 0.01 to 10 parts by weight per 100 parts by weight of wax A, and the amount of the antioxidant is 0.02 to 1 times the amount of the radical initiator. The manufacturing method according to any one of claims 4 to 10, characterized in that: