JPH0329104B2 - - Google Patents

Description

[Detailed description of the invention]

[] Object of the Invention The present invention relates to an olefinic polymer mixture.
More specifically, (A) an olefin polymer, (B) an organic compound having at least one unsaturated bond in the molecule and containing a hydroxyl group, (C) an organic peroxide, and (D) a glass fiber. , (E) mica and
(F) This relates to an olefinic polymer mixture consisting of an organic tin compound and/or a tertiary amine compound, which has extremely excellent adhesive properties and is useful when creating painted products, adhesives, and laminates of molded products. The object is to provide these articles which not only have good rigidity but also have improved warpage. [] Background of the Invention As is well known, olefin resins not only have excellent moldability but also have good properties such as mechanical strength, heat resistance, solvent resistance, and chemical resistance, so they are widely manufactured industrially. It is used as a general-purpose resin in many fields. However, since olefin resins do not have polar groups in their molecules (so-called non-polar), they are chemically extremely inactive polymeric substances. Furthermore, it not only has high solidity but also extremely low solubility in solvents, so when used in fields such as painting and adhesion, the paintability and adhesiveness are extremely low. As described above, olefin resins are used in fields where good adhesion and paintability are required (for example, automobile parts, home appliance parts) despite their excellent moldability and the above-mentioned properties. The use of ``was naturally limited.'' In order to solve the problems of adhesion and paintability of olefin resins, various methods have been proposed for some time, such as those described below. (a) A method in which an olefin resin or a molded product thereof is surface-treated from the outside and modified by a physical or chemical method (hereinafter referred to as the "modification method"). (b) A method of adding other polymeric substances or additives to olefin resin. Hereinafter, among these methods, the modification method will be explained in more detail and its problems will be described. This method includes "flame treatment method, plasma treatment method, ozone treatment method, corona discharge treatment method, and irradiation treatment method using ultraviolet rays or electron beams"
[Hereinafter referred to as "modification method (a)"] and "method of treatment using a chromic acid mixture and a mineral acid such as concentrated sulfuric acid, and crosslinking using a compound containing a polar group on the olefin resin or its molded product. A method of chemical treatment such as grafting in the presence or absence of an agent (hereinafter referred to as "modification method (b)") is mentioned. By these modification methods, chemically active sites rich in polar groups are provided on the surface of the olefinic resin or its molded product, and the surface is physically roughened. As a result, it is thought that the effects of improved paintability and adhesiveness can be obtained. However, in order to carry out this modification method (a), the shape of the molded object to be treated must be significantly limited, and furthermore, the treatment effect not only deteriorates significantly over time due to leaving it after treatment, but also In many cases, the degree of activation is not always sufficient. Moreover, it has disadvantages such as being economically disadvantageous because it requires various expensive processing equipment. In addition, among the modification methods (b), the treatment method using mineral acids not only tends to cause pollution due to the chemicals used, but also requires complicated post-treatment steps such as neutralization, water washing, and drying. be. Furthermore, chemical treatment methods such as grafting require a drying process, and detailed considerations such as monomer application and grafting atmosphere are also required.
Grafting reaction time is relatively long. Therefore,
It has drawbacks such as not being suitable for continuous production. As described above, the coating properties and adhesion can be improved to some extent by the modification method, but all methods have various drawbacks, so it is difficult to say that they are satisfactory improvement methods. Furthermore, as a method for imparting paintability and adhesion to the surface of olefin-based polymer molded products, we have developed polyolefin polymers in which chlorinated polypropylene or maleic anhydride is graft-polymerized onto the surface of the molded product before coating with paint or adhesive. A method has been developed to apply a primer whose main ingredients are:
However, with the method of applying primer,
The cost increases because the coating or adhesion process is added by one step. Including the above, without impairing the above-mentioned properties and processability of the olefin resin,
Olefinic polymers, modified products and mixtures thereof with good adhesion and paintability have not yet been developed. Based on these facts, the present inventors, in order to solve these drawbacks, (A) 100 parts by weight of an olefin polymer, (B) having at least one unsaturated bond in the molecule and having a hydroxyl group. Organic compounds contained
0.1 to 50 parts by weight, (C) 0.01 to 20 parts by weight of an organic peroxide, and (D) 0.05 to 10 parts by weight of an organic tin compound and/or a tertiary amine compound. We have previously proposed this method after discovering that it has no defects and adheres strongly regardless of the type of paint. However, when the resulting mixture was molded, the resulting molded product had unsatisfactory rigidity and warpage. [] Constitution of the Invention Based on the above, the present inventors aimed to produce an olefin polymer and an olefin polymer mixture that have excellent paintability and adhesion, and have improved rigidity and warpage of molded products. As a result of various searches, (A) olefin polymer (B) "organic compound that has at least one unsaturated bond in the molecule and contains a hydroxyl group (hereinafter referred to as "hydroxyl compound"), (C ) organic peroxide, (D) glass fiber, (E) mica, and (F) an organic tin compound and/or a tertiary amine compound, and the olefin polymer,
The mixture of glass fibers in the total amount of glass fibers and mica is 5 to 40% by weight, and the mixing ratio of mica is 5 to 40% by weight,
The mixing ratio of the olefin polymer is at least 40% by weight, and the mixing ratio of the hydroxyl compound is 0.1 to 50 parts by weight with respect to 100 parts by weight of the total amount of the olefin polymer, glass fiber, and mica, and the organic peroxide An olefinic polymer mixture containing 0.01 to 20 parts by weight of organic tin compounds and 0.005 to 10 parts by weight of organotin compounds and tertiary amine compounds has not only good adhesive properties but also excellent adhesive properties. The inventors have discovered that the resulting mixture has improved rigidity and warpage of molded products, and have arrived at the present invention. [] Effects of the invention If the mixture according to the invention is used, the following effects will be exhibited. (1) Excellent coatings or adhesives can be obtained without carrying out the above-mentioned modification of the surface as conventionally done. (2) Since a paint having an isocyanate group can be applied directly to the surface of a molded product without applying a primer in advance, a coated product with good oil resistance can be obtained. (3) Similar to (2), it can be easily bonded to various substances (for example, wood, various metals) because it firmly adheres to adhesives having isocyanate groups. (4) A laminate with polyurethane foam can be created at the same time as foaming is performed on the molded product using a method such as injection foaming. (5) It is ideal as a core material for various parts that require high rigidity and shape stability. Excellent coatings, adhesives and laminates can be obtained. The mixture obtained by the present invention can be used in a wide variety of ways to achieve the above effects. Typical usage examples are shown below. (1) Automotive parts such as bumpers, instrument panels, armrests, door liners, seat bags, duct covers, etc. (2) Home appliance parts such as the interior and exterior of coolers and refrigerators (3) Housing materials such as loop panels and insulation walls ( 4) Daily necessities and furniture such as dining tables, desk surfaces, furniture panels, kitchen cabinets, ice boxes, etc. (5) Freezer components such as interior materials for refrigerated trucks and freezer walls [] Specific description of the invention (A) Olefin polymer The olefinic polymers used in the present invention include ethylene homopolymers, propylene homopolymers, random or block copolymers of ethylene and propylene, and ethylene and/or propylene copolymers having at most 7 carbon atoms. Examples include random or block copolymers with other α-olefins (copolymerization ratio of α-olefins is at most 20% by weight). The molecular weight of these olefin polymers is generally
2 to 1 million, preferably 2 to 500,000,
Particularly suitable are olefin resins having a molecular weight of 50,000 to 300,000. In addition, low density (0.900 g/cm ³ ) to high density (0.980 g/cm ³ ) ethylene homopolymers, propylene homopolymers, random or block copolymers of ethylene and propylene, and copolymers of ethylene or propylene with other Random or block copolymers with α-olefins are preferred. These olefinic polymers are produced by using a catalyst system (so-called Ziegler catalyst) obtained from a transition metal compound and an organoaluminium compound, and by supporting a chromium compound (for example, chromium oxide) on a carrier (for example, silica). It is obtained by homopolymerizing or copolymerizing an olefin using the resulting catalyst system (so-called Phillips catalyst) or a radical initiator (eg, an organic peroxide). Furthermore, the present invention also includes modified polyolefins obtained by graft polymerizing these olefin polymers with a compound having at least one double bond (for example, an unsaturated carboxylic acid or a vinyl silane compound). The production methods for these olefin polymers and modified polyolefins are well known. These olefin polymers and modified polyolefins may be used alone or in combination of two or more. Furthermore, two or more of these olefin polymers and modified polyolefins may be used as a resin blend in any proportion. (B) Hydroxyl Compound The hydroxyl compound used in the present invention is a compound having at least one unsaturated bond (double bond, triple bond) and containing a hydroxyl group. Typical examples include alcohols with double bonds, alcohols with triple bonds, esters of monovalent or divalent unsaturated carboxylic acids and unsubstituted dihydric alcohols, and unsubstituted trihydric alcohols of unsaturated carboxylic acids. Examples include esters with hydrohydric alcohols, esters with unsubstituted tetrahydric alcohols, and esters with unsubstituted pentahydric or higher alcohols. Among the alcohols having a double bond, preferred representative examples are those whose general formula is represented by the following formula [formula ()]. In formula (), R ¹ and R ² may be the same or different, and have a hydrogen atom or a carbon number of 1 to 24
hydrocarbon groups. Representative examples of desirable alcohols having a triple bond are those whose general formula is represented by the following formula [formula ()]. (R ³ −C≡C−R ⁴ )−)OH () In the formula, R ³ and R ⁴ may be the same or different, and each has a hydrogen atom or a carbon number of 1 to 24
hydrocarbon groups. Further, the ester of an unsubstituted dihydric alcohol and an unsaturated carboxylic acid is an ester of a monovalent unsaturated carboxylic acid and an unsubstituted dihydric alcohol, and as a representative example of a preferable one, the general formula is the following formula [( ) is expressed by the following formula. In formula (), R ⁵ is an unsaturated hydrocarbon group having 2 to 24 carbon atoms, and R ⁶ is an unsaturated hydrocarbon group having 2 to 24 carbon atoms.
~24 hydrocarbon groups. Furthermore, the ester of an unsubstituted trihydric alcohol and an unsaturated carboxylic acid is an ester of a monovalent unsaturated carboxylic acid and an unsubstituted trihydric alcohol,
A typical example of a desirable one is one whose general formula is represented by the following formula [formula ()]. In formula (), R ⁷ is an unsaturated hydrocarbon group having 2 to 24 carbon atoms, and R ⁸ is an unsaturated hydrocarbon group having 2 to 24 carbon atoms.
~24 hydrocarbon groups. In addition, the ester of an unsubstituted tetrahydric alcohol and an unsaturated carboxylic acid is an ester of a monovalent unsaturated carboxylic acid and an unsubstituted tetrahydric alcohol, and a typical example of a preferable one is the general formula [() It is expressed by the following formula. In formula (), R ⁹ is an unsaturated hydrocarbon group having 2 to 24 carbon atoms, and R ¹⁰ is an unsaturated hydrocarbon group having 2 to 24 carbon atoms.
~24 hydrocarbon groups. Further, esters of unsubstituted pentavalent or higher alcohols and unsaturated carboxylic acids are esters of monovalent unsaturated carboxylic acids and unsubstituted pentavalent or higher alcohols, and representative examples of desirable ones include:
The general formula is expressed by the following formula [formula ()]. In the formula (), n is 4 or more, R ¹¹ is an unsaturated hydrocarbon group having 2 to 24 carbon atoms,
R ¹² is a hydrocarbon group having 2 to 60 carbon atoms. In addition, other esters include esters of unsaturated dihydric carboxylic acids and unsubstituted polyhydric alcohols, and preferred representative examples include those whose general formula is represented by the following formula [formula ()]. can give. In formula (), m is 1 or more, and R ¹³
is an unsaturated hydrocarbon group having 2 to 50 carbon atoms, and R ¹⁴ is a hydrocarbon group having 2 to 100 carbon atoms. Representative examples of these hydroxyl compounds include the specification of Japanese Patent Application No. 57-36502 and "Handbook of Existing Chemical Substances" (Kagaku Kogyo Nippo Co., Ltd.,
Published in 1974) Supervised by the Chemical Safety Division, Basic Industries Bureau, Ministry of International Trade and Industry, 2nd edition, pages 25, 27 to 28
Pages, pages 50 to 55 and pages 57 to 57
It is described on page 58. Among the hydroxyl compounds used in the present invention, representative examples of suitable ones include 3-
Hydroxy-1-propene, 4-hydroxy-
1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene,
3-hydroxy-2-methyl-1-bropene,
Cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pentene, cis-
1,4-dihydroxy-2-butene, trans-1,4-dihydroxy-2-butene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl Crotonate, 2,3,4,5,6-pentahydroxyhexyl acrylate, 2,3,4,5,6-pentahydroxyhermethacrylate, 2,3,
Examples include 4,5,-tetrahydroxypentyl acrylate and 2,3,4,5-tetrahydroxypentyl methacrylate. (C) Organic peroxide Furthermore, the organic peroxide used in the present invention is generally used as an initiator in radical polymerization and a crosslinking agent for polymers, and has a half-life of 1 minute or more at 100°C or more. A temperature of 130°C or higher is particularly preferred.
If the above-mentioned temperature is below 100°C, it is not only difficult to handle, but also the effect of using it is not very noticeable, so it is not desirable. Representative examples of preferred organic peroxides include ketone peroxides such as 1,1-bis-tertiary-butylperoxy-3,3,5-trimethylcyclohexane, dialkyl peroxides such as dicumyl peroxide, , 5-dimethylhexane-2,5-hydroperoxide, diacyl peroxides such as benzoyl peroxide, and peroxyesters such as 2,5-dimethyl-2,5-dibenzoyl peroxyhexane. It will be done. (D) Glass fiber The glass fiber used in the present invention usually has a single fiber diameter of 0.5 to 20 microns, particularly preferably 0.5 to 15 microns.
It is undesirable to use glass fibers with a single fiber diameter of less than 0.5 microns because they may break during kneading and molding. On the other hand, if the diameter exceeds 20 microns, it is difficult to improve the rigidity of the resulting mixture, which is not preferred. Also, the cut length is generally 0.03 to 15mm.
A thickness of 0.05 to 10 mm is particularly desirable. It is undesirable to manufacture the mixture using glass fibers with a cut diameter of less than 0.03 mm because it is difficult to improve the stiffness of the resulting mixture. On the other hand, if the diameter exceeds 15 mm, it is not preferable because it may break during kneading and molding. The glass fibers used in the present invention are commonly used as fillers or reinforcing agents in the rubber industry and synthetic resin industry, and include those made of vinyl acetate resin, silane compounds, or titanate compounds. Those subjected to coupling treatment can also be used. Furthermore, so-called milled glass fibers manufactured by grinding these glass fibers can also be used. (E) Mica Furthermore, mica, which is used together with flaky graphite in the present invention, is generally a naturally occurring platy mineral, and although its chemical composition is complex, it is mainly called muscovite, phlogopite, or biotite. It is something. The density is usually around 2.8g/ ^cm3 , and the average particle size is 1-100 microns, especially 2-100 microns.
50 microns are preferred in this invention. Further, it is desirable that the aspect ratio be 20 to 70 in order to exhibit the above-mentioned effects. (F) Organic tin compound Furthermore, examples of the organic tin compound used in the present invention include those represented by the following formula [() formula]. In formula (), R ¹⁵ , R ¹⁶ , R ¹⁷ and
R ¹⁸ may be the same or different, and is a hydrocarbon group with at most 12 carbon atoms, and Y ¹ and Y ² may be the same or different, and are monovalent or divalent carbon groups with at most 18 carbon atoms. Acids ^, derivatives of the carboxylic acids (alkyl esters), alcohols, mercaptans, mercapto acids. or an integer from 1 to 20. Typical examples of this organic tin compound include monobutyl tin trimethyl malate, dibutyl tin dilaurate, a mixture of dibutyl tin dimalate and dibutyl tin dimethyl maleate, dibutyl tin dioctyl maleate, and tribenzyl・Tin and trimethyl malate are listed. (G) Tertiary amine compound The tertiary amine compound used in the present invention is used as a catalyst in the curing reaction of urethane polyol and isocyanate. Typical examples include dimethylaminopropylamine, diethylaminopropylamine, tris(dimethylaminomethyl)phenol, tetraguanidine,
N,N-dibutylethanolamine, N-methyl-N,N-diethanolamine, 1,4-diazabicyclo(2,2,2)otane and 1,
Examples include 8-diazabicyclo(5,4,0)-7 undecene. (H) Mixing ratio In producing the mixture of the present invention, the mixing ratio of glass fiber in the total amount of olefin polymer, glass fiber, and mica is 5 to 40% by weight, preferably 5 to 35% by weight. , especially 10 to 35% by weight. If the mixing ratio of the glass fibers in the total amount of the olefin polymer, glass fibers and mica is less than 5% by weight, the stiffness of the resulting mixture cannot be improved. On the other hand, if more than 40 parts by weight is mixed, moldability will be poor when producing a molded product, and even if a molded product is produced, the appearance of the molded product will not be good. The mixing ratio of mica in the total amount of the olefinic polymer, glass fiber and mica is 5 to 40% by weight, preferably 5 to 35% by weight, and particularly preferably 10 to 35% by weight.
If the mixing ratio of mica in the total amount of the olefin polymer, glass fiber, and mica is less than 5% by weight, the stiffness of the resulting mixture cannot be improved. On the other hand, if the amount exceeds 40% by weight, moldability will be poor when producing a molded product, and even if a molded product is produced, the appearance of the molded product will not be good. Furthermore, the mixing proportion of the olefinic polymer in the total amount of the olefinic polymer, glass fiber and mica is at least 40% by weight, preferably 45% by weight or more, particularly 50% by weight.
The above is preferable. If the mixing ratio of the olefin polymer to the total amount of the olefin polymer, glass fiber, and mica is less than 40% by weight, it is difficult to produce a homogeneous mixture, and even if a homogeneous mixture is obtained. ,
Poor formability. In producing the mixture of the present invention, the mixing ratio of the hydroxyl compound is 0.1 to 50 parts by weight, and 0.2 to 30 parts by weight relative to 100 parts by weight of the olefin polymer, glass fiber, and mica. Preferably, especially 0.3-20
Parts by weight are preferred. If the mixing ratio of the hydroxyl compound to 100 parts by weight of the total amount (sum) of the olefinic polymer, glass fiber and mica is less than 0.1 part by weight, the effect of improving adhesion will be insufficient. On the other hand, even if 50 parts by weight or more is used, no improvement in adhesion is observed depending on the amount used, and rather the original properties of the olefin polymer are impaired, which is not preferable. In addition, 100 parts by weight of the total amount (total) of olefin polymer, glass fiber, and mica
The mixing ratio of the organic peroxide is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, and particularly preferably 0.1 to 7 parts by weight. If the mixing ratio of organic peroxide is less than 0.01 part by weight with respect to 100 parts by weight of the total amount (sum) of olefin polymer, glass fiber, and mica, not only will the effect of improving adhesion be low, but also the adhesion strength of the mixture will decrease. Durability also decreases. On the other hand, if the amount exceeds 20 parts by weight, the excellent mechanical properties originally possessed by the polymer will deteriorate, which is undesirable in any case. Furthermore, 100 parts by weight of an olefin polymer,
The mixing ratio of the organotin compound and the tertiary amine compound to the total amount (total sum) of the glass fiber and mica is 0.005 to 10 parts by weight, preferably 0.02 to 5 parts by weight, particularly 0.05 to 10 parts by weight. 3 parts by weight is preferred.
If the total mixing ratio of the organotin compound and tertiary amine compound is less than 0.005 parts by weight with respect to 100 parts by weight of the olefinic polymer, glass fiber, and mica,
Poor effect. On the other hand, even if more than 10 parts by weight is added, the effect will not be improved and, on the contrary, it may cause adverse effects such as bleeding. (J) Production of mixtures and molded products To produce the mixture of the present invention, an olefinic polymer, a hydroxyl compound, a glass fiber mica, an organic peroxide, an organotin compound and/or a tertiary amine compound are used. What is necessary is just to mix uniformly so that it may fall within the said mixing ratio range. In producing this composition, a part of the mixed components may be mixed in advance to produce a so-called masterbatch, and this masterbatch and the remaining mixed components may be mixed to produce the above-mentioned blended components. good. The mixture may also be composed of an olefinic polymer, a hydroxyl compound, a glass fiber, mica, an organic peroxide, an organic tin compound, and/or a tertiary amine compound, depending on the intended use of the mixture. In addition, the mixed ingredients include oxygen, heat and UV stabilizers, metal deterioration inhibitors, flame retardants, colorants,
Additives such as electrical property improvers, fillers, antistatic agents, lubricants, processability improvers, and tack improvers may be mixed as long as they do not impair the properties of the mixture of the present invention. good. This mixture may be dry blended using mixers commonly used in the olefinic polymer industry such as Henschel mixers, Banbury mixers, kneaders, roll mills, and screw extruders. It can also be produced by melt-kneading using a mixer. At this time, a more uniform mixture can be obtained by dry blending in advance and then melt-kneading the resulting mixture. In the case of melt kneading above,
If carried out at high temperatures, the olefinic polymer may deteriorate. However, the graft polymerization between the olefinic polymer and the hydroxyl compound must be carried out at a temperature at which the organic peroxide used is decomposed. From the above, although it differs depending on the type of organic peroxide used, this melt-kneading process is generally
Conducted at 160-300°C. Various molded articles may be produced from the composition thus produced by processing methods commonly used in the field of olefin polymers, such as extrusion molding, injection molding, and press molding. At this time, it is necessary to carry out the process at a temperature higher than the temperature at which the composition (graft material) obtained as described above melts. However, if the reaction is carried out at a considerably high temperature, the olefinic polymer may deteriorate, so it is a matter of course that the reaction must be carried out at a temperature below which decomposition occurs. (K) Coating and adhesion method Apply a coating material having an isocyanate group to the surface of the molded product obtained as described above to a thickness of 1 to 500 mm.
The object of the present invention can be achieved by uniformly applying the coating to a micron size (when dry). The application method is not a special method; it is sufficient to apply a method that is generally used on the surface of metal or synthetic resin molded objects. Typical methods include applying with a spray gun, and applying with a brush. Examples include a method of coating using a roll coater, and a method of coating using a roll coater. According to the present invention, it is possible to obtain a molded article that not only has excellent adhesion and gloss on the coated surface, but also has excellent weather resistance and gasoline resistance, such as in the case of urethane coating, so it is possible to obtain automotive parts. It can be applied to etc. In addition, metallization can be performed on the coated film having isocyanate groups.
It is also suitable for laminating different materials. Next, for bonding with an adhesive, an adhesive having an isocyanate group (for example, a solvent-based urethane adhesive, a water-based vinyl urethane adhesive) is applied to the surface of the obtained molded product, and the adhesive surface is coated with an adhesive having an isocyanate group. The adhesive body of the present invention can be obtained by bonding shapes of substances that can be bonded with an adhesive.
These materials include metals (e.g. aluminum, iron, copper, and their alloys), glass, paper, fibers,
Wood, leather, rubber (e.g. neoprene,
urethane rubber, butadiene rubber, natural rubber),
Examples include polar group-containing resins (eg, ABS resin, polyester, polyamide, polyacrylonitrile, and the above-mentioned olefin polymers). Shaped objects include thin objects (for example, foils, papers, films), sheet-like objects, board-like objects, plate-like objects, pipe-like objects, rod-like objects, container-like objects, spherical objects, and box-like objects. ,
Other examples include those with complicated shapes. Furthermore, it is not limited to two layers, and multiple layers are also possible. Furthermore, as for polyurethane foam, the laminate of the present invention can be produced by simultaneously carrying out the urethane polymer production reaction and foaming on the surface of the molded product. In manufacturing this laminate, no special equipment or special method is required. That is, foaming methods such as injection foaming, mold foaming, and spray foaming that are commonly used in the field of polyurethane foam production may be applied. Furthermore, the polyol, isocyanate compound, blowing agent, etc. used as raw materials for the polyurethane foam do not need to be special materials, and any commonly used materials may be used without any limitation. In addition, in the conventional methods of performing the above-described coating, adhesion, and lamination, the surface of the molded product may be cleaned or degreased in the previous step. The main purpose of this is to remove surface stains caused by oils and fats, eliminate variations in adhesion, and further improve adhesion. Specific examples include wiping off using an organic solvent such as isopropyl alcohol, toluene, or trichlene, or for large molded items, immersing the molded item in such an organic solvent under heating, or treating it with heated steam. I can give you a method. These degreasing and cleaning steps can be similarly applied to the molded product obtained according to the present invention. Furthermore, the same effects as before can be expected without being affected in any way. [] Examples and Comparative Examples The present invention will be explained in more detail below using Examples. In addition, in the examples and comparative examples, melt
The index (hereinafter referred to as "MI") is JISK-
According to 6760, temperature is 190℃ and load is 2.16
Measured under Kg conditions. In addition, the melt flow index (hereinafter referred to as "MFI") is based on JIS K-
According to 6758, temperature is 230℃ and load is 2.16
Measured under Kg conditions. In addition, for the paint film peel strength test, a test piece with a width of 10 mm is cut out from the A test piece, and a part of the paint film is forcibly peeled off from one end of the test piece, and then a part of the paint film is forcibly peeled off from one end of the test piece. Using a tensile testing machine, the tensile speed was 50 mm/min.
The coating film was peeled off under the conditions of a peeling angle of 180 degrees and a temperature of 20°C, and the coating peel strength (g/10
mm). Furthermore, gasoline resistance is
A cross cut was made at an angle of 30 degrees using an NT cutter, and each test piece was immersed in gasoline at room temperature (approximately 20°C) for 24 hours, and changes in the coating surface were observed. In addition, for water resistance, a cross cut was made in the same way as the gasoline resistance test piece, and each test piece was immersed in lukewarm water at 40°C for 240 hours.
Changes in the coating surface were observed. Furthermore, the adhesive strength of the molded product of the olefin-based polymer mixture is 10 cm x 2 cm.
It was cut out into a short piece, and adhesive was applied to the end of the piece in a 3 cm x 2 cm area. A molded product of the olefin polymer composition obtained in the example or comparative example, a copper plate, or a piece of wood was attached to this adhesive part, and the tensile shear stress at breakage was It was measured. Furthermore, the adhesion strength between the molded product and the polyurethane foam was determined by forming the polyurethane foam between flat test pieces arranged in parallel at 1 cm intervals by an injection foaming method. A sample was cut into a size of 1 cm, and the upper and lower molded parts of the sample were held between the crosshead of a tensile tester, and the tensile speed was set at 5 mm/cm in the direction perpendicular to the contact surface.
The sample was pulled under conditions of 10 minutes, and the strength when the sample broke was measured and defined as adhesion strength (Kg/cm ² ). Also,
Stiffness is measured using flexural modulus, ASTM D
-790. Furthermore, warpage was evaluated by forming a disk with a thickness of 2.3 mm and a diameter of 125 mm with a center gate having a diameter of 1 mm, and measuring the maximum amount of deformation. In addition, in the examples and comparative examples, the mixed components olefin polymer, glass fiber,
Mica, hydroxyl compounds, organic peroxides,
The organic tin compounds and tertiary amine compounds used were those whose physical properties and types are shown below. [Propylene homopolymer] Density is 0.900 g/cm ³ as an olefin polymer
A propylene homopolymer [hereinafter referred to as "PP(1)"] having the following properties and an MFI of 4.0 g/10 minutes was used. [Block propylene copolymer] Also, as an olefin polymer, the ethylene content is 12.0% by weight, and the MFI is 2.0g/10
A propylene-ethylene block copolymer (hereinafter referred to as "PP(2)") having a density of 0.900 g/cm ³ and a density of 0.900 g/cm 3 was used. [High-density ethylene homopolymer] Furthermore, as an olefin polymer, the density is 0.96.
g/cm ³ and a high density ethylene homopolymer (hereinafter referred to as "HDPE") with an MI of 20 g/10 min.
was used. [Glass fiber] As the glass fiber, a glass fiber (hereinafter referred to as "GF") with a single fiber diameter of 11 microns and a cut length of 3 mm was used. [Mica] As mica, the average particle diameter was 7 microns. ,
I used mica with an aspect ratio of 30. [Hydroxyl compound] As a hydroxyl compound, 2-hydroxyethyl acrylate [hereinafter referred to as "compound (A)]",
2-hydroxypropyl methacrylate [hereinafter referred to as "compound (B)"] and 3,6-dimethyl-
4-octyne-3,6-diol [hereinafter referred to as “compound
(C)” was used. [Organic peroxide] Benzoyl peroxide (hereinafter referred to as "BPO") and dicumyl peroxide (hereinafter referred to as "DCP") were used as organic peroxides. [Organic tin compounds] As organic tin compounds, dibutyl tin malate [hereinafter referred to as "compound (1)]" and dibutyl tin laurate [hereinafter referred to as "compound (2)]"
It was used. [Tertiary amine compound] Furthermore, as a tertiary amine compound, 1,4
-Diazabicyclo[2,2,2]octane [hereinafter referred to as "compound (3)"] was used. Examples 1 to 10, Comparative Examples 1 to 10 The components whose amounts are shown in Table 1 were mixed in advance for 10 minutes using a super mixer. Each mixture obtained was processed using a vented extruder (diameter
Pellets were manufactured while kneading using a 50 mm). Each pellet obtained was injection molded using a 5 oz. injection molding machine at a temperature of 230°C.
A flat specimen (120 x 150 mm, 2 mm thick) was prepared. One side of each specimen thus obtained was coated with a two-component urethane paint (manufactured by Nippon P Chemical Co., Ltd., trade name: R).
Two types of -2572R-263 enamel were sprayed using a spray gun to a thickness of 35 to 40 microns for a paint film peeling test. Next, heat drying was performed at a temperature of 90° C. for 30 minutes. After leaving the sample at room temperature for one day and night, a peel strength test of the coating film of each sample was conducted. The results are shown in Table 2. Furthermore, each was tested for gasoline resistance and water resistance. The results are shown in Table 2. In addition, in these tests, the state of change in the coating film is shown below. ○ No change at all, △ Partial peeling, × Fully peeling After cutting the above flat specimen into short pieces of 10 cm x 2 cm, a two-component room temperature curing solvent-based polyurethane adhesive (Konishi) was applied. (manufactured by Chuo Rika Kogyo Co., Ltd., product name, BOND KU-10) and a two-component curing water-based vinyl urethane adhesive (manufactured by Chuo Rika Kogyo Co., Ltd., product name, RIKABOND CR-100), and cut it into short pieces of the same size. Samples of the resin parts used in the Examples and Comparative Examples [hereinafter referred to as "(A)"], copper plates [1 mm thick, hereinafter referred to as "(B)]", or wood (lauan wood, 5 mm thick) were used. , hereinafter referred to as "(C)"] and left at room temperature for 24 hours, the adhesive strength was measured.The results are shown in Table 3.Each test obtained as described above Two pieces were fixed in parallel with an interval of 1 cm, and polyurethane foam was produced between them by injection foaming.
As the equipment for injection foaming and the stock solution of polyurethane foam, Insulvac #20 (trade name) manufactured by Instaform Co., Ltd. (USA) was used (foaming ratio: 40 times). After being left for 24 hours after injection, the adhesion strength of each specimen to the polyurethane foam was measured. The results are shown in Table 2. In addition, in this test, if the adhesion strength is too strong and failure does not occur at the interface between the molded part and the polyurethane foam part, and the polyurethane foam suffers cohesive failure, the "cohesive failure" column in Table 3 will be added. ”.

【table】

【table】

【table】

【table】

【table】

[Table] In Comparative Examples 8 to 10, normal strands could not be obtained during kneading using a vented extruder, and it was impossible to take them off. Comparative Example 11 A composition consisting of 60 parts by weight of PP(1), 20 parts by weight of GF and 20 parts by weight of mica was injection molded in the same manner as above to produce a flat specimen. A thermosetting polypropylene primer (manufactured by Nippon P Chemical Co., Ltd., trade name BR-291,
○Using a spray gun, spray the primer evenly to a film thickness of 13 to 15 microns, and then
Heat drying was carried out at a temperature of 30 minutes. Next, apply a two-component urethane paint to this primer-coated surface in the same manner as above, and apply it at a temperature of 90℃ for 30 minutes.
Drying was performed by heating for a minute. The peel strength of this coating is
It was 170g/cm. A water resistance test was conducted, but no change in the paint film could be observed. However, when we conducted a gasoline resistance test,
The paint film completely peeled off. Furthermore, a two-component cold-curing polyurethane adhesive (Bond KU-10) was applied to the primer-coated surface prepared in the same manner as above, and the above (A), (B), or (C) was applied. Place it on the specimen at room temperature.
After leaving it for 24 hours, the adhesive strength was measured. The adhesive strength is 2.5Kg/cm ² in (A), 2.7Kg/cm ² in (B) and
In (C), it was 2.6Kg/cm ² .

Claims (1)

[Scope of Claims] 1 (A) an olefin polymer, (B) an organic compound having at least one unsaturated bond in its molecule and containing a hydroxyl group, (C) an organic peroxide, (D ) glass fiber, (E) mica, and (F) a mixture consisting of an organotin compound and/or a tertiary amine compound, and the olefin polymer,
The mixing ratio of glass fibers in the total amount of glass fibers and mica is 5 to 40% by weight, and the mixing ratio of mica is 5 to 40% by weight, but the mixing ratio of olefin polymer is at least 5% to 40% by weight.
The mixing ratio is 0.1 to 50 parts by weight of the organic compound containing a hydroxyl group, and 40 parts by weight of the organic compound containing a hydroxyl group, and 40 parts by weight of the organic compound containing the hydroxyl group, and
0.01 to 20 parts by weight, and the total amount of the organic tin compound and tertiary amine compound is 0.005 to 20 parts by weight.
10 parts by weight of an olefinic polymer mixture.