JPS59184246A - Olefin polymer mixture - Google Patents

Abstract

PURPOSE:To provide the titled mixture which has excellent adhesiveness and gives moldings having good rigidity, by mixing a hydroxyl group-contg. compd., an org. peroxide, an organotin compd. or a tert. amine compd. and glass fiber with an olefin polymer. CONSTITUTION:The titled compsn. comprising an olefin polymer (A), an org. compd. (B) having an OH group and an unsaturated bond per molecule (e.g. 3- hydroxy-1-propene), an org. peroxide (C), an organotin compd. (e.g. monobytyltin trimethylmalate) and/or a tert. amine compd. (e.g. dimethylaminopropylamine) (D) and glass fiber (E), wherein component D accounts for 5-40wt% of the combined quantity of component A and E, and the quantity of component B is 0.1-50pts.wt., that of component C is 0.01-20pts.wt. and that of component D is 0.05-10pts.wt. per 100pts.wt. of the combined quantity of components A and E. The mixture gives moldings having good rigidity and exhibits very excellent adhesion in coating, bonding and laminating the moldings.

Description

[Detailed description of the invention] (1) Purpose of the invention The present invention relates to olefinic polymer mixtures.

More specifically, (N olefin polymer, (E) organic compound having at least one unsaturated bond in the molecule and containing a hydroxyl group, (Q organic peroxide, (
D) It relates to an olefinic polymer mixture consisting of an organic tin compound and/or a tertiary amine compound and (E) glass fiber, and is useful for creating painted products, adhesives, and laminates of molded products. 9. The object is to provide a mixture which has extremely good adhesive properties and good rigidity of molded products.

(6) Background of the Invention As is well known, olefin resins not only have excellent moldability, but also have good properties such as mechanical strength, side heat resistance, solvent resistance, and chemical resistance, so they are widely used industrially. It has been manufactured and used in a wide range of applications as a general-purpose resin. However, olefin resins are polymeric substances that are chemically extremely inert because they have many polar groups in their molecules (so-called non-polar). Furthermore, it not only has high crystallinity but also extremely low solubility in solvents, so when used in fields such as painting and adhesion, it has very low paintability and adhesiveness.

As mentioned above, although olefin resins have excellent moldability and the above-mentioned properties, they are used in fields where good adhesion and paintability are required (FC, for example, automobile parts, home appliance parts). The use of olefin resins naturally had limitations.

In order to solve the problems of adhesion and paintability of olefin resins, various methods as described below have been proposed for quite some time.

゛・9(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 "modification method").

(b) A method of adding other polymeric substances or additives to the olefin resin.

Below, among these methods, the denaturation 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 ``denaturation method (a)''.
”] and ``a method of treatment using a chromic acid mixture and a mineral acid such as concentrated sulfuric acid, and a method of treating an olefin resin or its molded product with a compound containing a polar group, etc. to determine the presence or absence of a crosslinking agent T1. A method of chemical treatment such as grafting (hereinafter referred to as "denaturation method (b)") is mentioned below.

These modification methods provide the surface of the olefin resin or its molded product with chemically active extrasites rich in polar groups, and also physically roughen the surface. 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 extremely limited, and furthermore, the treatment effect not only deteriorates significantly over time but also deteriorates after treatment. In many cases, the degree of activation is not always sufficient. Second, it has disadvantages such as being economically disadvantageous because it requires various expensive processing equipment.

In addition, among the edible methods (b), the treatment method using mineral acids not only tends to cause the chemicals used to be a source of pollution, but also requires complicated post-treatment steps such as neutralization, washing, and drying. be. Furthermore, chemical treatment methods such as grafting require a drying process, and not only do they require careful consideration of the monomer application and grafting atmosphere, but also require a relatively long gland reaction time. . Therefore, it has drawbacks such as not being suitable for continuous production.

As described above, although it is possible to improve the paintability and adhesion by using the modification method, it is difficult to say that it is a satisfactory improvement method because each method has various drawbacks.

Furthermore, as a method for imparting paintability and adhesion to the surface of molded olefin polymer products, chlorinated polypropylene or maleic anhydride was graft-polymerized onto the surface of the molded product before coating with paint or adhesive. A method of applying a primer containing polyolefin or the like as a main component has been developed.

However, the method of applying the brimer increases the cost by adding one additional step of application or adhesion.

Including the above, olefinic polymers, modified products and mixtures thereof that do not have 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 as a result, (A) Olefin polymers. , (B) "has at least one unsaturated bond in the molecule,
and an organic compound containing a hydroxyl group (hereinafter referred to as a "hydroxyl compound"), (0) an organic peroxide, (I)) an organic tin compound and/or a tertiary amine compound, and (1) It is a mixture consisting of glass fibers, and the mixing ratio of glass fibers in the total amount of the olefin polymer and glass fibers is 5 to 40% by weight, which is the golden rule between olefin polymers and glass fibers. The mixing ratio for 100 parts by weight is such that the hydroxyl compound is 01 to 50 parts by weight, the organic peroxide is 001 to 20 parts by weight, and the organic tin compound and tertiary amine compound are
The inventors have discovered that an olefin polymer mixture containing 0.01 to 10 parts by weight as the maximal amount has the above-mentioned drawbacks and can firmly adhere to the paint regardless of the type of paint, and has thus arrived at the present invention.

Effects of the existing invention If the mixture according to the present invention is used, the following effects will be exhibited.

(1) An excellent coating or adhesive can be obtained without carrying out the above-mentioned modification of the surface as conventionally done.

(2) Since a paint having an inocyanate group can be applied directly to the surface of a molded product without applying a brimer 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 inocyanate 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 product can be obtained.

The mixture obtained according to the present invention can be used in a wide variety of ways to achieve the above-mentioned effects.

Typical usage examples are shown below.

(1) Automotive parts such as Hamper 7, instrument panels, armrests, door liners, seat packs, duct covers, etc. (2) Home appliance parts such as the interior and exterior of coolers and refrigerators (3) Residential use such as loop panels, insulation walls, etc. Materials (4
) Daily necessities and furniture such as dining tables, desk surfaces, furniture panels, kitchen cabinets, ice boxes, etc. (5) Recesses in freezer parts such as refrigerated truck interiors and freezer walls Detailed Description of the Invention (A) Olefin Polymer This Invention The olefinic polymers used include ethylene homopolymers, propylene homopolymers, random or block copolymers of ethylene and propylene, and ethylene and/or propylene with as many carbon atoms as possible. Examples include random or block copolymers with seven other α-olefins (copolymerization ratio of α-olefins is at most 20% by weight). The molecular weight of these olefin polymers is generally from 20,000 to 1,000,000, preferably from 20,000 to 500,000, and particularly preferably from 50,000 to 30,000. Also, low density (0,900
f/ca) or high density (0,980g/ca)
Preferred are ethylene homopolymers, propylene homopolymers, random or block copolymers of ethylene and propylene, and random or block copolymers of ethylene or propylene with other α-olefins.

These olefin polymers can be obtained by supporting a catalyst system (so-called Ziegler catalyst) obtained from a transition metal compound and an organoaluminum compound, a carrier (for example, silica), or a chromium compound (for example, chromium oxide). It is obtained by homopolymerization or copolymerization of olefins using catalyst systems (so-called Phillips divisions) or radical initiators (e.g. organic peroxides).

Furthermore, the present invention also includes modified polyolefins obtained by graft polymerizing a compound having at least one double bond (for example, an unsaturated carboxylic acid or a vinyl silane compound) to these olefin polymers.

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 ratio.

(13) Hydroxyl compound The hydroxyl compound used in the present invention has at least one unsaturated bond (double bond, triple bond),
and is a compound containing a hydroxyl group. Typical examples include alcohols with double bonds, alcohols with triple bonds, esters of -valent or divalent unsaturated carboxylic acids and unsubstituted dihydric alcohols, and unsaturated carboxylic acids and unsubstituted dihydric alcohols. Examples include esters with substituted trihydric alcohols, esters with unsubstituted tetrahydric alcohols, and esters with unsubstituted trihydric or higher alcohols.

As representative examples of preferable alcohols having double bonds, the general formula is the following formula [formula (■)] (I), R1 and R2 may be the same or different, and the number of hydrogen atoms or carbon atoms is 1 to 24 hydrocarbon groups.

Representative examples of desirable alcohols having a triple bond are those represented by the general formula (formula 70).

(R6-03O-R' +Of(Ql) (In Yubu, R3 and R4 may be the same or different, and are a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms.

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 a typical example of a preferable one is the general formula of the following formula [ (2)].

In the formula @), 几5 is an unsaturated hydrocarbon group having 2 to 24 carbon atoms, and R' is a hydrocarbon group having 2 to 24 carbon atoms.

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, and a typical example of a desirable one has the general formula [( ■) Formula].

In formula (IV), R' is an unsaturated hydrocarbon group having 2 to 24 carbon atoms, and R8 is a hydrocarbon group having 2 to 24 carbon atoms.

In addition, the ester of an unsubstituted tetrahydric alcohol and an unsaturated carbonic 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 [ (V)].

In formula (V), R9 is an unsaturated hydrocarbon group having 2 to 24 carbon atoms, and R10 is a hydrocarbon group having 2 to 24 carbon atoms.

Furthermore, esters of unsubstituted trihydric or higher alcohols and unsaturated carbonic acids are esters of monovalent unsaturated carboxylic acids and unsubstituted trihydric or higher alcohols. The general formula is expressed by the following formula [formula (b)].

In formula (b), n is 4 or more, and 11 is an unsaturated 11 hydrocarbon group having 2 to 24 carbon atoms, p:, , B
+2 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 a typical preferred example is the general formula of the following formula [(6)
The following expression can be mentioned.

1 1 ) In the formula, m is 1 or more, R15 is an unsaturated hydrocarbon group having 2 to 50 carbon atoms, and R14 is a hydrocarbon group having 2 to 100 carbon atoms.

Representative examples of these hydroxyl compounds include Japanese Patent Application No. 57-36502 and No. 57-49'06.
Each item in No. 5 is a list of existing chemical substances... (Kagaku Kogyo Nippo, published in 1978) Supervised by the Basic Inter-Industrial Chemical Safety Division, Ministry of International Trade and Industry, 2nd edition, p. 25, 27th
Pages 28 to 28, 50 to 55 and 5
It is described on pages 7 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-
Fan, 3-hydroquine-2-methyl-1-propene,
cis-5-hydroxy-2-pentene, trans-5-
Hydroxy-2-pentene, cis-I+・4-dihydroxy-2-butene, trans-1,4-dihydroxy-
2-butene, 2-hydroquine ethyl acrylate, 2-
Hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxopropyl methacrylate, 2-hydroquinethyl crotonate, 2,3.4
, 5.6-pentahydroxyhexyl mecryl), 2
．． 3,4°5,6-pentahydroxyhexyl methacrylate), 2,3,4,5-tetrahydroquine pentyl methacrylate and 2,3,4,5-tetrahydroquine pentyl methacrylate.

(0) 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.
A temperature of 130°C or higher is preferred, particularly a temperature of 130°C or higher. If the above-mentioned temperature is below 100° C., it is not desirable because it is not only difficult to handle, but also the effect of using it is not recognized. Representative examples of preferred organic peroxides include 1,1-bis-tertiary-
Butyl peroxides such as 3,3,5-trimethylcyclohexane, dialkyl peroxides such as dicumyl peroxide, and 2,5-dimethylhexane-2,5-trimethylcyclohexane. Diacylno-hydrochloroxide, such as penzoylbaroquinide, and 2,5-dimethyl-
Examples include peroquine esters such as 2,5-dibenzoylperoquine hexane.

(D) Organic tin compound Furthermore, examples of the organic tin compound used in the present invention include those represented by the following formula [formula (4)].

In formula (e), R15, B16. p, +7 and Bj[] may be the same or different, and have at most 1 carbon number.
The two hydrocarbon groups υ yl and Y2 may be the same or different, and include monovalent or divalent carboxylic acids having at most 18 carbon atoms, derivatives of the carboxylic acids (alkyl esters), alcohols, mercaptans, Xl, which is a mercapto acid, is a carboxylic acid group having an oxygen atom, a sulfur atom, and a double bond having at most 4 carbon atoms, and t is 0 or an integer of 1 to 20.

Typical examples of these organic tin compounds include motuputyl tin trimethyl malate, diptyl tin dilaurate, mixtures of diptyl tin cimarate and diptyl tin dimethyl malate, diptyl tin dioctyl malate, and tribenzyl.・Tin and trinotyl male 7 are listed.

(Odor) Tertiary amine compound The tertiary amine compound used in the present invention is a catalyst used in the curing reaction of urethane polyol and incyanate.

Typical examples include dimethylaminopropylamine,
Diethylaminepropylamine, tris(dimethylaminomethyl)phenol, tetraguanidine, N,N-diptylethanolamine, N-methyl-N,N-jetanolamine, 1,4-diazabicyclo(2,2,2)
Othane and 118-diazabicyclo(5,4,'o)
- Clandesene is mentioned.

(F) Graph fiber A thickness of 0.5 to 15 microns is preferable.

It is undesirable to use glass fibers with a single fiber diameter of less than 0.5 microns because they may break during cross-wiring or 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.

In addition, the cut length is generally 003 to 1'5 m, with 005 to 10 birds being particularly desirable. The diameter is 00
It is undesirable to manufacture the mixture using less than 3 Wn of glass fiber, as it is difficult to improve the stiffness of the resulting mixture. On the other hand, if it exceeds 15 rolls, it is not preferable because it may break during kneading and molding.

The glass fin resin used in the present invention is commonly used as a filler or reinforcing agent in the rubber industry and the synthetic resin industry, and it may be a mixture of vinyl acetate resin, silane compound, or A compound treated with a titanate compound can also be used. So-called milled glass fibers produced 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 olefin polymer and glass fiber is preferably 5 to 40% by weight, preferably 5 to 35% by weight. In particular, 10 to 35 weight JfA, % is suitable. The mixing ratio of glass fiber in the total amount of olefin polymer and glass fiber is 5 Jft.
If it is less than 1, the stiffness of the resulting mixture cannot be improved. On the other hand, if more than 30 overlapping parts are 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 total amount of 100 parts by weight of olefinic polymer and glass fiber (
The mixing ratio of hydroquine compounds to the total amount is 01
~50 parts by weight, preferably 02 to 30 parts by weight, and preferably 3 to 20 parts by weight. If the mixing ratio of the hydroquine compound is less than 0.1 parts by weight with respect to the total amount of olefin polymer and glass fiber of 100 parts by weight, the effect of improving adhesion is insufficient. On the other hand, even if 50 parts by weight or more is used, the effect of improving adhesion depending on the amount used is not observed, and rather the original properties of the olefin polymer are impaired, which is not preferable.

In addition, the total amount of olefin polymer and glass fiber (100 parts by weight) The mixing ratio of the organic peroxide used in the taillight is 0.
The amount is preferably from 0.01 to 20 parts by weight, preferably from 0.05 to 10 parts by weight, and preferably from 0.1 to 7 parts by weight. 100
If the mixing ratio of organic peroxide to the total amount of olefin polymer and glass fiber is less than 0 or 0 parts by weight, the effect of improving adhesion will not be low, but the adhesion strength of the mixture will be less durable. Sexuality 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, 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 0005 to 10 parts by weight, and 002 to 5 parts by weight. Parts 005 to 3 are particularly preferred. If the mixing ratio of the organotin compound and the tertiary amine compound to 100 parts by weight of the total amount 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, the effect will not be improved and, on the contrary, there may be adverse effects such as bleeding.

(+-1) Production of mixture and molded product In order to produce the mixture of the present invention, an olefin polymer, a hydroxy compound, an organic peroxide, an organic tin compound and/or a tertiary amine compound, and a glass fiber are used. may be uniformly mixed within the above mixing ratio range. To produce this composition, a part of the mixed components is mixed in advance to produce a so-called masterbatch, and this masterbatch and the mixed components of the upper frame are produced to form the above-mentioned blended components. Mixtures may also be produced.

The mixture may also be composed of an olefin polymer, a hydroxy compound, an organic peroxide, an organotin compound and/or a tertiary amine compound, and glass fiber, depending on the intended use of the mixture. Mixed components include oxygen, heat and UV stabilizers, metal deterioration inhibitors, flame retardants, colorants, electrical property improvers, fillers, antistatic agents, lubricants, and processability improvers. Additives such as tack modifiers and adhesion modifiers may be incorporated to the extent that they do not impair the properties of the mixture of the present invention.

To produce this mixture, triblending may be performed 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 such as a blender. At this time, a more uniform mixture can be obtained by triblending in advance and further melt-kneading the resulting mixture.

In the case of the above melt-kneading 9, if carried out at a high temperature, the olefin polymer may deteriorate. However, it is necessary to perform the graft polymerization at a temperature at which the organic peroxide used to graft polymerize the olefin polymer and hydroxy compound is decomposed. As described above, this melting and kneading is generally carried out at 16°C to 30°C, although it varies depending on the type of organic peroxide used.

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 olefin polymer may deteriorate, so it is natural that the reaction must be carried out at a temperature below which decomposition occurs.

(, J) Coating and adhesion method The present invention is achieved by uniformly coating the surface of the molded product obtained as described above with a coating material having an isocyanate group to a thickness of 1 to 500 microns (when dry). can achieve the objectives of The application method is not a special method, and it is sufficient to apply a method commonly 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 coating method and a method of applying using a roll coater.

Honsha r! According to AK, for example, in the case of urethane coating, it is possible to obtain molded products with excellent adhesion and good gloss on the coated surface, as well as excellent weather resistance and gasoline resistance, making it suitable for automotive parts. It can be applied to etc.

Further, it is also suitable to utilize the applied coating film having an incyanate group and to further metallize it or to laminate different materials thereon.

Next, for bonding with an adhesive, an adhesive having an incyanate 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 By the liquid groove agent! The bonded body of the present invention can be obtained by bonding shapes of bondable substances.

These materials include metals (e.g. aluminum, iron, copper, and their alloys), glass, paper, textiles, wood, leather,
Examples include rubbers (for example, neoprene rubber, urethane rubber, butadiene rubber, natural rubber), and polar group-containing resins (for example, 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, vibrator-like objects, rod-like objects, container-like objects, spherical objects, and foil-like objects. objects, and other things with complex shapes. Furthermore, it is not limited to two C1 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,
If a foaming method such as an injection foaming method, a mold foaming method, or a spray foaming method which is commonly used in the field of manufacturing polyurethane foam is applied, 1: Yes. Furthermore, the polyol, incyanate compound, blowing agent, etc. used as raw materials for polyurethane foam do not need to be special, and any commonly used ones may be used without any limitation.

Hiko, in the conventional methods of performing the above-mentioned 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 a method of wiping off using an organic solvent such as isopropyl alcohol, toluene, or trichlene; or, for large molded products, a method of crushing the molded product in such an organic solvent under heating, or a method of treating it with heated steam. can give. These degreasing and O-cleaning steps can be similarly applied to molded articles obtained according to the present invention.

Furthermore, it is completely unaffected and the same effects as before can be expected.

EXAMPLES AND COMPARATIVE EXAMPLES The present invention will be explained in more detail with reference to Examples below.

In addition, in the examples and comparative examples, the melt index (hereinafter referred to as [M, T, j) is JrSK, -67
According to 60, the temperature is 190℃ and the load is 2.16
Measured under the condition of Kg. In addition, the flow index (hereinafter referred to as "MFTj")
According to K-6758, a test piece with a temperature of 23" was cut out, and after forcibly peeling off a portion of the coating from one end of the test piece, it was tested using a tensile testing machine used in tensile testing of plastics, etc. The coating was peeled off for 11 minutes under the conditions of a tensile speed of 50 mm/min, a peel angle of 180 degrees, and a temperature of 20 degrees Celsius, and the peel strength of the coating film (S' 710
mm)・Furthermore, the gasoline resistance is determined by the coating surface V
A cross cut was made at an angle of 30 degrees using a CN"r cuckoo, and after each test piece was immersed in gasoline for 24 hours at room temperature (approximately 20 degrees Celsius), changes in the coating surface were observed. Similarly to the gasoline-resistant test pieces, the test pieces were immersed in lukewarm water at 40°C for 240 hours, and changes in the coating surface were observed. The molded product of the olefin polymer mixture was cut into short strips of 1 (ICm x 2 m), and an adhesive of 3 Cm x 2 CTn was applied to the ends. The molded product of the olefin polymer composition obtained in the comparative example or a copper plate or a piece of wood was laminated together at a tensile rate of 50 min.
? Tensile at IImZ minute, and measure the bow 1 tension shear stress at the time of failure fc. 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 with an interval of ICrn by the injection foaming method, and then using this sandwich-like test. A piece of ICmXICTnO was cut into large grooves to be used as a sample, and the upper and lower molded parts of the sample were held between the crosshead of a tensile testing machine and the tensile speed was set at 5 mm/cm in the direction perpendicular to the contact surface.
The strength when the sample breaks after being tensed under the conditions of
lT was set at 11, and the adhesion strength was determined as (K9/a4).

Olefin polymers, hydroxyl compounds, glass fibers, used in Examples and Comparative Examples
The physical properties and types of organic peroxides, organic tin compounds, and tertiary amine compounds are shown below.

[Propylene homopolymer]

As an olefin polymer, the density is 0.900 y/a
A propylene homopolymer (hereinafter referred to as "PP(1)J") having a molecular weight of 4.0 f and a M I''I of 4.0 f 710 minutes was used.

"Block propylene copolymer" 1. As a cleaved olefin polymer, the ethylene content ratio is 1.2.0, and the MFI is 2.
0 g710 min and a density of 0.900 f/c
A propylene-ethylene bronoch copolymer (hereinafter referred to as PP(2)J), which is rd, was used.

[Low density ethylene homopolymer]

Further 1 (density as olefin polymer is 09xrf
? /cd Aji and M, 1. A low-density ethylene homopolymer (hereinafter referred to as "LDPE") having a particle diameter of 5.1 iP/10 minutes was used.

[Hydroxyl compound]

As hydroxyl compounds, 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 (0)"] was used.

[Glass fiber]

As a glass fiber, the single fiber diameter is 11 microns.
), glass fiber with a cut length of 3 (hereinafter referred to as "GF")
) was used.

[Organic peroxide]

As organic peroxides, benzoyl peroxide [hereinafter referred to as "BPOJ"] and dicumyl peroxide [
Hereinafter referred to as j'-D OPI] was used.

[Organic tin compound]

As the organic tin compounds, dibutyl tin malate (hereinafter referred to as "compound (1)") and dibutyl tin laurate (hereinafter referred to as "compound (2)") were used.

[Tertiary amine compound]

Further, as a tertiary amine compound, 1,4-diazapicyclo[2,2,2','1-octane [hereinafter referred to as compound (3')] was used.

Examples 1 to 12 and Comparative Examples 1 to 7 The ingredients whose amounts are shown in Table 7 were mixed in advance for 10 minutes using a super mixer. Each of the obtained mixtures was kneaded using a vented extruder (diameter: 50 mm) to produce pellets. Each of the obtained pellets was injection molded using a 5-ounce injection molding machine at a temperature of 230°C to form a flat specimen (120×150.
, 2 mm thick).

A two-component urethane paint (manufactured by Nippon B Chemical Co., Ltd., trade name R-257) was applied to one side of each specimen thus obtained using a spray gun to a thickness of 35 to 40 microns for a paint film peeling test. I sprayed it. Then, 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 these tests, the state of change in the coating film is shown below.

○ No change at all, △ Partial peeling, × Fully peeling, 10c1n? After cutting into a 2-on strip, apply a two-component room temperature curing solvent type polyurethane adhesive (manufactured by Konishi Co., Ltd., product name, Bond KTJ-
10) and two-component curing water-based vinyl urethane adhesive (
Manufactured by Chuo Rika Kogyo Co., Ltd., product name, Rikabond 0R-100
) was used to cut a 1f cut into a short piece of the same size.
Hereinafter referred to as "(4)"], copper plate [thickness: 1 mm, hereinafter referred to as r
(B) J] or woody
．． IIm (hereinafter referred to as r (0) J)], and after standing at room temperature for 24 hours, the adhesive strength was measured.

The results are shown in Table 3.

Two test pieces obtained as described above were fixed in parallel at a distance of 1 m, and polyurethane foam was produced between them by injection foaming.

The equipment for injection foaming and the raw solution for polyurethane foam are manufactured by Instaform Inc. (USA) under the trade name Insulvac#
20 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. However, 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, and the polyurethane foam suffers cohesive failure, the density X (strength Write “cohesive failure” in the column.

Table 2 (Part 1) Table 2 (Part 2) In Comparative Example 7, a normal strand could not be obtained during kneading using a vented extruder, and it was impossible to take it off.

Comparative Example 8 A mixture consisting of parts by weight of PP(])8'O and 20 parts by weight of GF was injection molded in the same manner as above to produce a flat specimen. One side of this sample was coated with a thermosetting polypropylene primer (manufactured by Nippon B Chemical Co., Ltd., trade name:
After uniformly spraying the film with a spray gun to a film thickness of 13 to 15 microns, the film was dried by heating at a temperature of 90° C. for 30 minutes. Next, a two-component urethane coating was applied to the brimer-coated surface in the same manner as described above, and heat-dried at 90° C. for 30 minutes. The peel strength of this coating film is shown in Table 2. I conducted a water-based test, but could not detect any change in the paint film. but.

We conducted many tests on gasoline cutting properties. those results as a second
Shown in the table. 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 section sample (5), copper plate (B), and wood was measured. 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 by the present invention is molded into a molded product and the surface of the molded product is coated with so-called urethane, urethane adhesive, or J-urethane, the peel strength is 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 only a small amount of an organic tin compound and/or a tertiary amine compound, not only the strength of these compounds is greatly improved, but also the rigidity (flexural modulus) of the resulting molded product is improved.
It is also clear that improvements have been made in terms of

Patent applicant: Showa Denko Co., Ltd. Representative Patent Attorney Sei Kikuchi

Claims (1)

[Scope of Claims] (A) an olefin polymer, (B) an organic compound having at least one unsaturated bond in the molecule and containing a hydroxyl group, (0)
A mixture consisting of an organic peroxide, (D) an organic tin compound and/or a tertiary amine compound, and (IC) glass fiber, and the glass fiber accounts for the total amount of the olefin polymer and glass fiber. The mixing ratio is 5 to 40%, and the metal content of olefin polymer and glass fiber is t-, pi+-, 1o.
The mixing ratio of the organic compound containing a hydroxyl group to the weight G part is 0.01 to 50 parts by weight, the fan oxide is 0.01 to 20 parts by weight, and the organic tin compound and the tertiary amine are mixed. The total amount of system compounds is 0.05 to 10
Parts by weight of the olefinic polymer mixture.