JPH0352763B2 - - Google Patents

Description

[Detailed description of the invention]

[] Object of the Invention The present invention relates to an olefinic polymer mixture.
More specifically, (A) olefin polymer, (B) organic compound having at least one unsaturated bond in the molecule and containing a hydroxyl group, (C) organic peroxide, (D) organic tin This product relates to an olefinic polymer mixture consisting of a chemical compound and/or a tertiary amine compound and (E) glass fiber, and has extremely excellent adhesive properties when making painted products, adhesives, and laminates of its molded products. The purpose of this invention is to provide a mixture having good rigidity in a molded product. () Background of the Invention As is well known, olefin resins not only have excellent moldability, but also have excellent mechanical strength, heat resistance,
Because it has good properties such as solvent resistance and chemical resistance, it is widely manufactured industrially and used in many fields as a general-purpose resin. however,
Olefin resins are chemically extremely inactive polymeric substances because they do not have polar groups in their molecules (so-called non-polar). 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 mentioned above, although olefin resins have excellent moldability and the above-mentioned properties, olefin resins are used in fields where good adhesiveness and paintability are required (for example, automobile parts, home appliance parts). The use of resin 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 of externally surface-treating an olefin resin or molded product and modifying it by physical or chemical methods (hereinafter referred to as the "modification method") (b) Adding other polymeric substances to the olefin resin Or how to add additives. Hereinafter, among these methods, the modification method will be explained in more detail and 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 mineral acid such as concentrated sulfuric acid, and crosslinking using a compound containing a polar group in an olefin resin or its 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 olefin 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 is significantly limited, and furthermore, the treatment effect is not only significantly reduced over time due to being left after the treatment, but also In many cases, the degree of activation due to treatment 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 mentioned above, although the modification methods can improve the paintability and adhesion to some extent, it is difficult to say that they are satisfactory improvement methods because each method has various drawbacks. 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 increases. Including the above, olefinic polymers, modified products and mixtures thereof that do not impair the above-mentioned properties and processability of olefinic polymers and have good adhesiveness and paintability have not yet been developed. [] Structure of the Invention Based on the above, the present inventors have conducted various searches for producing olefin polymers and olefin polymer mixtures with excellent paintability and adhesive properties, and have found that (A) olefin polymers (B) "Organic compound having at least one unsaturated bond in the molecule and containing a hydroxyl group (hereinafter referred to as "hydroxyl compound"), (C) Organic peroxide, (D) Organic It is a mixture consisting of a tin compound and/or a tertiary amine compound and (E) glass fiber, and the proportion of the glass fiber in the total amount of the olefin polymer and glass fiber is 5 to 40% by weight. Yes, total amount of olefin polymer and glass fiber
The mixing ratio for 100 parts by weight is 0.1 to 50 parts by weight of the hydroxyl compound, and 0.1 to 50 parts by weight of the organic peroxide.
0.01 to 20 parts by weight, and the total amount of the organic tin compound and tertiary amine compound is 0.01 to 20 parts by weight.
The present invention was achieved by discovering that 10 parts by weight of an olefin polymer mixture does not have the above-mentioned drawbacks and adheres strongly to paints regardless of the type. [] 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 by applying the coating, adhesion, or injection foaming described above, it has good oil resistance and high rigidity. A molded article having the following characteristics 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 pads, and duct covers (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 olefin polymer used in the present invention includes ethylene homopolymers, propylene homopolymers, random or block copolymers of ethylene and propylene, and Examples include random or block copolymers of ethylene and/or propylene and other α-olefins having at most 7 carbon atoms (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,
Olefin resins having a weight of 50,000 to 300,000 are sometimes suitable. 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 has at least one unsaturated bond (double bond,
It is a compound that has a triple bond) and contains a hydroxyl group. Typical examples include alcohols with double bonds, alcohols with triple bonds, esters of mono- or divalent unsaturated carboxylic acids and unsubstituted dihydric alcohols, and esters of unsaturated carboxylic acids with unsubstituted dihydric alcohols. 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 include the general formula [()
It is expressed by the following 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 −) () In the formula (), R ³ and R ⁴ may be the same or different, and have 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. Furthermore, the 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 formula (), n is 4 or more, and R ¹¹
is an unsaturated hydrocarbon group having 2 to 24 carbon atoms, and 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 specifications of Japanese Patent Application Nos. 57-36502 and 57-49065, as well as "Handbook of Existing Chemical Substances" (Kagaku Kogyo Nippo, published in 1974), published by the Ministry of International Trade and Industry for Basic Industries. Supervised by the Bureau of Chemical Stability Division, 2nd edition, vol.
Page 25, pages 27 to 28, pages 50 to 55
and pages 57 to 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-propene,
Cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pentene, cyc-
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-pentahydroxyhexyl methacrylate, 2,
Mention may be made of 3,4,5-tetrahydroxybentyl 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) 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. An acid, a derivative (alkyl ester) of the carboxylic acid, an alcohol, ^a mercaptan, a mercapto acid. 0 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. (E) Tertiary amine compound The tertiary amine compound used in the present invention is a catalyst used 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,
8-Diazabicyclo(5,4,0)-koundecene is mentioned. (F) Graph Iver 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. If a mixture is manufactured using glass fibers with a cut diameter of less than 0.03 mm, it is undesirable because it is difficult to improve the stiffness of the resulting mixture.On the other hand, if a glass fiber with a cut diameter of more than 15 mm is used, This is not desirable because it may break during 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. In addition, so-called milled glass fibers manufactured by grinding these glass fibers can also be used. (G) Mixing ratio In producing the mixture of the present invention, the mixing ratio of glass fiber in the total amount of olefinic polymer and glass fiber is 5 to 40% by weight, preferably 5 to 35% by weight, particularly Ten
~35% by weight is preferred. If the mixing ratio of the glass fibers in the total amount of the olefin polymer and the glass fibers is less than 5% by weight, the stiffness of the resulting mixture cannot be improved. On the other hand, if more than 30 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. In producing the mixture of the present invention, the mixing ratio of the hydroxyl compound to 100 parts by weight of the olefin polymer and glass fiber is 0.1 to 50 parts by weight, and 0.2 to 50 parts by weight.
30 parts by weight is preferred, particularly 0.3 to 20 parts by weight. If the mixing ratio of the hydroxyl compound is 0.1 part by weight or less with respect to the total amount of olefin polymer and glass fiber of 100 parts by weight,
Adhesion improvement effect is 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, the mixing ratio of organic peroxide to the total amount of olefin polymer and glass fiber of 100 parts by weight is 0.01 to 20 parts by weight, and 0.05 to 20 parts by weight.
10 parts by weight is desirable, and 0.1 to 7 parts by weight is particularly preferred. If the mixing ratio of organic peroxide is less than 0.01 part by weight with respect to the total amount of olefinic polymer and glass fiber (100 parts by weight), not only the effect of improving adhesion is low, but also the durability of the adhesion strength of the mixture is reduced. do. 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. Further, the mixing ratio of the organotin compound and the tertiary amine compound to the total amount of olefin polymer and glass fiber of 100 parts by weight is 0.005 to 10 parts by weight, and 0.02 to 5 parts by weight. Part is preferable, especially 0.05~
3 parts by weight is preferred. If the mixing ratio of the organotin compound and the tertiary amine compound to the total amount of 100 parts by weight of the olefin polymer and glass fiber is less than 0.005 parts by weight, the effect will be poor. On the other hand, even if more than 10 parts by weight is added to Kari, the effect will not improve.
On the contrary, it may cause adverse effects such as bleeding. (H) Production of mixture and molded product In order to produce the mixture of the present invention, the olefinic polymer, hydroxyl compound, organic peroxide, organotin compound and/or tertiary amine compound and glass fiber are added as described above. They may be mixed uniformly within the range of mixing ratio. 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. Further, the mixture may be composed of an olefinic polymer, a hydroxyl compound, an organic peroxide, an organic tin compound and/or a tertiary amine compound, and a glass fiber, depending on the purpose of use of the mixture. The mixed components further include oxygen, heat and UV stabilizers, metal deterioration inhibitors, flame retardants, colorants, electrical property improvers, fillers, antistatic agents, lubricants,
Additives such as processability modifiers and tack modifiers may be incorporated to the extent that they do not impair the properties of the mixture of the present invention. 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, it must be carried out at a temperature at which the organic peroxide used to graft polymerize the olefin polymer and hydroxy compound is decomposed. From the above, although it differs depending on the type of organic peroxide used, this melt-kneading is generally performed at 160%
Performed at ~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. (J) Coating and adhesion method Apply paint 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 a molded article that is used in automobile parts. It can be applied to etc. Further, it is also suitable to utilize the applied coating film having isocyanate groups and further metallize it, or laminate different materials thereon. 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 the adhesive. The adhesive body of the present invention can be obtained by bonding shapes of substances that can be bonded with an adhesive. These substances include metals (e.g. aluminum, iron, copper, and their alloys);
Glass, paper, fibers, wood, leather, rubbers (e.g., neoprene rubber, urethane rubber, butadiene rubber, natural rubber), polar group-containing resins (e.g., ABS resin, polyester, polyamide,
Examples include polyacrylonitrile and the above-mentioned olefin polymers. In addition, 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 foil-like objects. , and others with complex 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, polyols used as raw materials for polyurethane foam,
The isocyanate compound, the blowing agent, etc. do not need to be special, and any commonly used ones may be used without any limitation. In addition, when performing the above-mentioned coating, adhesion, and lamination, the conventional methods
In the preceding step, the surface of the molded article may be cleaned or degreased. 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 them in such an organic solvent under heating, or treating them with heated steam. I can give you a method. These degreasing and washing 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 now be described in more detail with reference to Examples. In addition, in the examples and comparative examples, melt
The index (hereinafter referred to as "MI") is JIS K-
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 strip of 10 mm wide was cut out from the test piece.
After forcibly peeling off a portion of the coating film from one end of the specimen, a tensile tester used for tensile testing of plastics was used at a tensile speed of 50 mm/min, a peeling angle of 180 degrees, and a temperature of 20 degrees Celsius. Paint film peeling strength (g/10mm) when the paint film is peeled off under the following conditions:
And so. Furthermore, gasoline resistance is achieved by using NT on the coating surface.
After making a cross cut with a cutter at an angle of 30 degrees and immersing each test piece in gasoline at room temperature (approximately 20°C) for 24 hours, changes in the coating surface were observed. Also, for water resistance, a cross cut was made in the same way as the gasoline resistance test piece, and after each test piece was immersed in 40°C lukewarm water for 240 hours, changes in the coating surface were observed. Furthermore, the adhesive strength was determined by cutting out a molded product of the olefin polymer mixture into short strips of 10 cm x 2 cm, and applying adhesive to the ends of the strips in a 3 cm x 2 cm area. The 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 the 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 ). The physical properties and types of the olefin polymer, hydroxyl compound, glass fiber, organic peroxide, organic tin compound, and tertiary amine compound used in the Examples and Comparative Examples 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. [Low-density ethylene homopolymer] Furthermore, as an olefin-based polymer, the density
A low density ethylene homopolymer (hereinafter referred to as "LDPE") having a weight of 0.917 g/cm ³ and an MI of 5.1 g/10 minutes was used. [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. [Glass Fiber] As the glass fiber, a glass fiber (hereinafter referred to as "GF") having a single fiber diameter of 11 microns and a cut length of 3 mm 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 compound] As the organic tin compound, dibutyl tin malate [hereinafter referred to as "compound (1)]" and dibutyl tin laurate [hereinafter referred to as "compound (2)"] were used. [Tertiary amine compound] Furthermore, as a tertiary amine compound, 1,4
-Diazapicyclo[2,2,2]octane [hereinafter referred to as "compound (3)"] was used. Examples 1 to 12, Comparative Examples 1 to 7 The ingredients 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
50 mm) to produce pellets while kneading. 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).
-257) was 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). Cut specimens of the resin part used in each Example or Comparative Example [hereinafter referred to as "(A)"], copper plate [thickness 1 mm, hereinafter referred to as "(B)"], or wood (lauan wood, thickness 5 mm (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. Two test 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 3. 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. ”.

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[Table] In Comparative Example 7, normal strands could not be obtained during kneading using a vented extruder, and it was impossible to take off the strands. Comparative Example 8 A mixture consisting of 80 parts by weight of PP(1) and 20 parts by weight of GF 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., product name RB-291, modified primer) was sprayed onto one side of this specimen uniformly using a spray gun so that the film thickness was 13 to 15 microns. After that, at a temperature of 90℃
Heat drying was performed for 30 minutes. Next, a two-component urethane paint was applied to the primer-coated surface in the same manner as described above, and heat-dried at a temperature of 90°C for 30 minutes. The peel strength of this coating film is shown in Table 2. A water resistance test was conducted, but no change was observed in the paint film. However, a gasoline resistance test was conducted. The results are shown in Table 2.
Furthermore, as in Example 1, using a room-temperature curing polyurethane adhesive and a two-component curing water-based vinyl urethane adhesive, the adhesive strength between the resin part specimen (A), copper plate (B), and wood was measured. In addition, the adhesion strength of polyurethane foam produced by injection foaming was measured. The results are shown in Table 3. From the results of the above Examples and Comparative Examples, when the mixture obtained according to the present invention is molded into a molded product, and the surface of the molded product is coated with urethane, urethane adhesive, and urethane foamed, the peel strength and It is clear that not only the adhesive strength and adhesion strength are improved, but also the oil resistance and water resistance of the coating film are excellent. Furthermore, by adding small amounts of organic tin compounds and/or tertiary amine compounds, not only the strength of these compounds is greatly improved, but also the rigidity (flexural modulus) of the resulting molded products is improved. It is also clear that there are.

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 ) A mixture consisting of an organic tin compound and/or a tertiary amine compound and (E) glass fiber, and the proportion of the glass fiber in the total amount of the olefin polymer and glass fiber is 5 to 40% by weight. %, and the mixing ratio with respect to 100 parts by weight of the total amount of the olefinic polymer and glass fiber is 0.1 to 50 parts by weight of the organic compound containing a hydroxyl group,
An olefinic polymer mixture containing an organic peroxide in an amount of 0.01 to 20 parts by weight, and a total amount of an organic tin compound and a tertiary amine compound in an amount of 0.05 to 10 parts by weight.